diff --git a/django/db/models/query.py b/django/db/models/query.py
index 159c17d305..3d954fdf5c 100644
--- a/django/db/models/query.py
+++ b/django/db/models/query.py
@@ -210,9 +210,19 @@ class ValuesIterable(BaseIterable):
         if query.selected:
             names = list(query.selected)
         else:
+            # RemovedInDjango60Warning: place extra(select) entries at the
+            # beginning of the SELECT clause until it's completely removed.
+            extra_names = []
+            annotation_select = []
+            for alias, expression in query.annotation_select.items():
+                if isinstance(expression, _ExtraSelectFirstRawSQL):
+                    extra_names.append(alias)
+                else:
+                    annotation_select.append(alias)
             names = [
+                *extra_names,
                 *query.values_select,
-                *query.annotation_select,
+                *annotation_select,
             ]
         indexes = range(len(names))
         for row in compiler.results_iter(
@@ -250,9 +260,19 @@ class NamedValuesListIterable(ValuesListIterable):
             names = queryset._fields
         else:
             query = queryset.query
+            # RemovedInDjango60Warning: place extra(select) entries at the
+            # beginning of the SELECT clause until it's completely removed.
+            extra_names = []
+            annotation_select = []
+            for alias, expression in query.annotation_select.items():
+                if isinstance(expression, _ExtraSelectFirstRawSQL):
+                    extra_names.append(alias)
+                else:
+                    annotation_select.append(alias)
             names = [
+                *extra_names,
                 *query.values_select,
-                *query.annotation_select,
+                *annotation_select,
             ]
         tuple_class = create_namedtuple_class(*names)
         new = tuple.__new__
@@ -275,6 +295,17 @@ class FlatValuesListIterable(BaseIterable):
             yield row[0]
 
 
+# RemovedInDjango60Warning
+class _ExtraSelectFirstRawSQL(RawSQL):
+    """
+    Internal RawSQL subclass used during the deprecation of extra(select) to
+    preserve the undocumented implicit ordering of members at the begining of
+    the SELECT clause.
+    """
+
+    implicitly_select_first = True
+
+
 class QuerySet(AltersData):
     """Represent a lazy database lookup for a set of objects."""
 
@@ -1724,8 +1755,6 @@ class QuerySet(AltersData):
                 category=RemovedInDjango60Warning,
                 stacklevel=2,
             )
-            # XXX: This is mising the logic to always place extras at the begining
-            # of the select clause.
             if select_params:
                 param_iter = iter(select_params)
             else:
@@ -1739,7 +1768,9 @@ class QuerySet(AltersData):
                     if pos == 0 or entry[pos - 1] != "%":
                         entry_params.append(next(param_iter))
                     pos = entry.find("%s", pos + 2)
-                clone.query.add_annotation(RawSQL(entry, entry_params), name)
+                clone.query.add_annotation(
+                    _ExtraSelectFirstRawSQL(entry, entry_params), name
+                )
         if where:
             warnings.warn(
                 "extra(where) usage is deprecated, use filter() with RawSQL instead.",
diff --git a/django/db/models/sql/compiler.py b/django/db/models/sql/compiler.py
index 91e941837a..5c3166748d 100644
--- a/django/db/models/sql/compiler.py
+++ b/django/db/models/sql/compiler.py
@@ -262,9 +262,22 @@ class SQLCompiler:
             }
         selected = []
         if self.query.selected is None:
+            # RemovedInDjango60Warning: place extra(select) entries at the
+            # beginning of the SELECT clause until it's completely removed.
+            leading_annotation_select = []
+            annotation_select = []
+            if self.query.values_select_all:
+                for alias, expression in self.query.annotation_select.items():
+                    if getattr(expression, "implicitly_select_first", False):
+                        leading_annotation_select.append((alias, expression))
+                    else:
+                        annotation_select.append((alias, expression))
+            else:
+                annotation_select = self.query.annotation_select.items()
             selected = [
+                *leading_annotation_select,
                 *((None, col) for col in cols),
-                *self.query.annotation_select.items(),
+                *annotation_select,
             ]
         else:
             for alias, expression in self.query.selected.items():
diff --git a/tests/extra_regress/tests.py b/tests/extra_regress/tests.py
index 55075a82bb..095e4a76cb 100644
--- a/tests/extra_regress/tests.py
+++ b/tests/extra_regress/tests.py
@@ -286,7 +286,7 @@ class ExtraRegressTests(TestCase):
                     select={"foo": "first", "bar": "second", "whiz": "third"}
                 ).values_list()
             ),
-            [(obj.pk, "first", "second", "third", "first", "second", "third")],
+            [("first", "second", "third", obj.pk, "first", "second", "third")],
         )
 
         # Extra columns after an empty values_list() are still included
@@ -296,7 +296,7 @@ class ExtraRegressTests(TestCase):
                     select={"foo": "first", "bar": "second", "whiz": "third"}
                 )
             ),
-            [(obj.pk, "first", "second", "third", "first", "second", "third")],
+            [("first", "second", "third", obj.pk, "first", "second", "third")],
         )
 
         # Extra columns ignored completely if not mentioned in values_list()
diff --git a/tests/queries/tests.py b/tests/queries/tests.py
index 57b8b1b22a..46d6539974 100644
--- a/tests/queries/tests.py
+++ b/tests/queries/tests.py
@@ -2841,7 +2841,7 @@ class ValuesQuerysetTests(TestCase):
         self.assertEqual(type(values).__name__, "Row")
         self.assertEqual(
             values._fields,
-            ("id", "num", "other_num", "another_num", "num2", "id__count"),
+            ("num2", "id", "num", "other_num", "another_num", "id__count"),
         )
         self.assertEqual(values.num, 72)
         self.assertEqual(values.num2, 73)