diff --git a/src/cattrs/strategies/_unions.py b/src/cattrs/strategies/_unions.py
index 14add983..f75a641a 100644
--- a/src/cattrs/strategies/_unions.py
+++ b/src/cattrs/strategies/_unions.py
@@ -5,7 +5,7 @@
 
 from .. import BaseConverter
 from .._compat import get_newtype_base, is_literal, is_subclass, is_union_type
-from ..typealiases import is_type_alias
+from ..typealiases import get_type_alias_base, is_type_alias
 
 __all__ = [
     "configure_tagged_union",
@@ -174,7 +174,11 @@ def configure_union_passthrough(
     .. versionchanged:: 25.2.0
         Introduced the `accept_ints_as_floats` parameter.
     """
-    args = set(union.__args__)
+
+    def get_passthrough_base(type: Any) -> Any:
+        return get_type_alias_base(type) if is_type_alias(type) else type
+
+    args = {get_passthrough_base(type) for type in union.__args__}
 
     def make_structure_native_union(exact_type: Any) -> Callable:
         # `exact_type` is likely to be a subset of the entire configured union (`args`).
@@ -194,9 +198,10 @@ def make_structure_native_union(exact_type: Any) -> Callable:
         }
 
         non_literal_classes = {
-            get_newtype_base(t) or t
+            get_newtype_base(t) or get_passthrough_base(t)
             for t in exact_type.__args__
-            if not is_literal(t) and ((get_newtype_base(t) or t) in args)
+            if not is_literal(t)
+            and ((get_newtype_base(t) or get_passthrough_base(t)) in args)
         }
 
         # We augment the set of allowed classes with any configured subclasses of
@@ -211,7 +216,8 @@ def make_structure_native_union(exact_type: Any) -> Callable:
         spillover = {
             a
             for a in exact_type.__args__
-            if (get_newtype_base(a) or a) not in non_literal_classes
+            if (get_newtype_base(a) or get_passthrough_base(a))
+            not in non_literal_classes
             and not is_literal(a)
         }
 
@@ -273,7 +279,9 @@ def contains_native_union(exact_type: Any) -> bool:
                 for lit_arg in t.__args__
             }
             non_literal_types = {
-                get_newtype_base(t) or t for t in type_args if not is_literal(t)
+                get_newtype_base(t) or get_passthrough_base(t)
+                for t in type_args
+                if not is_literal(t)
             }
 
             return (literal_classes | non_literal_types) & args
diff --git a/tests/strategies/test_union_passthrough_695.py b/tests/strategies/test_union_passthrough_695.py
new file mode 100644
index 00000000..7e430ed2
--- /dev/null
+++ b/tests/strategies/test_union_passthrough_695.py
@@ -0,0 +1,21 @@
+from dataclasses import dataclass
+
+from cattrs import BaseConverter
+from cattrs.strategies import configure_union_passthrough
+
+
+@dataclass
+class DataClass:
+    field: str
+
+
+def test_type_alias_union_member(converter: BaseConverter) -> None:
+    """Native union passthrough handles PEP 695 aliases in the exact union."""
+    type NewScalar = str
+
+    configure_union_passthrough(str | int, converter)
+
+    assert converter.structure("value", NewScalar | DataClass) == "value"
+    assert converter.structure({"field": "value"}, NewScalar | DataClass) == DataClass(
+        "value"
+    )