diff --git a/django/db/models/sql/compiler.py b/django/db/models/sql/compiler.py
index 11ad4fde90..e311b7998a 100644
--- a/django/db/models/sql/compiler.py
+++ b/django/db/models/sql/compiler.py
@@ -347,10 +347,16 @@ class SQLCompiler:
                 continue
 
             if not self.query.extra or col not in self.query.extra:
-                # 'col' is of the form 'field' or 'field1__field2' or
-                # '-field1__field2__field', etc.
-                order_by.extend(self.find_ordering_name(
-                    field, self.query.get_meta(), default_order=asc))
+                if self.query.combinator and self.select:
+                    # Don't use the first model's field because other
+                    # combinated queries might define it differently.
+                    order_by.append((OrderBy(F(col), descending=descending), False))
+                else:
+                    # 'col' is of the form 'field' or 'field1__field2' or
+                    # '-field1__field2__field', etc.
+                    order_by.extend(self.find_ordering_name(
+                        field, self.query.get_meta(), default_order=asc,
+                    ))
             else:
                 if col not in self.query.extra_select:
                     order_by.append((
diff --git a/docs/releases/3.2.1.txt b/docs/releases/3.2.1.txt
index e8361e7370..2a7dda13ab 100644
--- a/docs/releases/3.2.1.txt
+++ b/docs/releases/3.2.1.txt
@@ -14,3 +14,8 @@ Bugfixes
 * Fixed a bug in Django 3.2 where subclasses of ``BigAutoField`` and
   ``SmallAutoField`` were not allowed for the :setting:`DEFAULT_AUTO_FIELD`
   setting (:ticket:`32620`).
+
+* Fixed a regression in Django 3.2 that caused a crash of
+  ``QuerySet.values()/values_list()`` after ``QuerySet.union()``,
+  ``intersection()``, and ``difference()`` when it was ordered by an
+  unannotated field (:ticket:`32627`).
diff --git a/tests/queries/test_qs_combinators.py b/tests/queries/test_qs_combinators.py
index 3b8204645d..351a401902 100644
--- a/tests/queries/test_qs_combinators.py
+++ b/tests/queries/test_qs_combinators.py
@@ -5,7 +5,7 @@ from django.db.models import Exists, F, IntegerField, OuterRef, Value
 from django.test import TestCase, skipIfDBFeature, skipUnlessDBFeature
 from django.test.utils import CaptureQueriesContext
 
-from .models import Number, ReservedName
+from .models import Celebrity, Number, ReservedName
 
 
 @skipUnlessDBFeature('supports_select_union')
@@ -234,6 +234,24 @@ class QuerySetSetOperationTests(TestCase):
             operator.itemgetter('num'),
         )
 
+    def test_union_multiple_models_with_values_list_and_order(self):
+        reserved_name = ReservedName.objects.create(name='rn1', order=0)
+        qs1 = Celebrity.objects.all()
+        qs2 = ReservedName.objects.all()
+        self.assertSequenceEqual(
+            qs1.union(qs2).order_by('name').values_list('pk', flat=True),
+            [reserved_name.pk],
+        )
+
+    def test_union_multiple_models_with_values_list_and_order_by_extra_select(self):
+        reserved_name = ReservedName.objects.create(name='rn1', order=0)
+        qs1 = Celebrity.objects.extra(select={'extra_name': 'name'})
+        qs2 = ReservedName.objects.extra(select={'extra_name': 'name'})
+        self.assertSequenceEqual(
+            qs1.union(qs2).order_by('extra_name').values_list('pk', flat=True),
+            [reserved_name.pk],
+        )
+
     def test_count_union(self):
         qs1 = Number.objects.filter(num__lte=1).values('num')
         qs2 = Number.objects.filter(num__gte=2, num__lte=3).values('num')