diff --git a/xarray/core/dataarray.py b/xarray/core/dataarray.py
index fc8edb1473c..562314e1b17 100644
--- a/xarray/core/dataarray.py
+++ b/xarray/core/dataarray.py
@@ -3060,6 +3060,19 @@ def unstack(
         >>> arr.identical(roundtripped)
         True
 
+        Notes
+        -----
+        **Sort order**
+
+        When the stacked dimension's ``MultiIndex`` was created by pandas (for
+        example, by wrapping a ``pd.Series`` with a ``pd.MultiIndex``), pandas
+        stores ``MultiIndex.levels`` in **sorted order** regardless of
+        insertion order.  In that case the coordinates of the new dimensions
+        after unstacking will also be sorted.  When the ``MultiIndex`` was
+        created by :py:meth:`DataArray.stack`, xarray preserves insertion
+        order instead.  Use :py:meth:`DataArray.sel` after unstacking to
+        select a specific order if needed.
+
         See Also
         --------
         DataArray.stack
diff --git a/xarray/core/dataset.py b/xarray/core/dataset.py
index 1ce84904623..dfe6a105248 100644
--- a/xarray/core/dataset.py
+++ b/xarray/core/dataset.py
@@ -5624,6 +5624,19 @@ def unstack(
         unstacked : Dataset
             Dataset with unstacked data.
 
+        Notes
+        -----
+        **Sort order**
+
+        When the stacked dimension's ``MultiIndex`` was created by pandas (for
+        example, by wrapping a ``pd.DataFrame`` or ``pd.Series`` with a
+        ``pd.MultiIndex``), pandas stores ``MultiIndex.levels`` in **sorted
+        order** regardless of insertion order.  In that case the coordinates
+        of the new dimensions after unstacking will also be sorted.  When the
+        ``MultiIndex`` was created by :py:meth:`Dataset.stack`, xarray
+        preserves insertion order instead.  Use :py:meth:`Dataset.sel` after
+        unstacking to select a specific order if needed.
+
         See Also
         --------
         Dataset.stack
diff --git a/xarray/tests/test_dataarray.py b/xarray/tests/test_dataarray.py
index 377fd2f8a8b..2817b81afc6 100644
--- a/xarray/tests/test_dataarray.py
+++ b/xarray/tests/test_dataarray.py
@@ -2811,6 +2811,32 @@ def test_stack_unstack_decreasing_coordinate(self) -> None:
         actual = stacked.unstack("allpoints")
         assert_identical(orig, actual)
 
+    def test_unstack_coords_are_sorted(self) -> None:
+        # When a DataArray is built from a pandas MultiIndex (e.g. from a
+        # pandas Series), pandas always stores MultiIndex.levels in sorted
+        # order regardless of insertion order.  Consequently, the coordinates
+        # of the new dimensions after unstack() are sorted, not in the
+        # original insertion order.
+        #
+        # This is distinct from xarray's own stack(), which preserves
+        # insertion order via factorize() for non-monotonic inputs.
+        arrays: list[np.ndarray] = [
+            np.array(["c", "a", "b"]),
+            np.array([1, 0, 0]),
+        ]
+        midx = pd.MultiIndex.from_arrays(arrays, names=["x", "y"])
+        s = pd.Series([10, 20, 30], index=midx, name="val")
+
+        da = DataArray(s, dims="z")
+        unstacked = da.unstack("z")
+
+        # pandas sorted the MultiIndex levels, so unstacked coords are sorted
+        assert list(unstacked["x"].values) == ["a", "b", "c"]
+        assert list(unstacked["y"].values) == [0, 1]
+
+        # use .sel() to restore a specific order
+        assert list(unstacked.sel(x=["c", "a", "b"])["x"].values) == ["c", "a", "b"]
+
     def test_unstack_pandas_consistency(self) -> None:
         df = pd.DataFrame({"foo": range(3), "x": ["a", "b", "b"], "y": [0, 0, 1]})
         s = df.set_index(["x", "y"])["foo"]