diff --git a/pandas/core/reshape/merge.py b/pandas/core/reshape/merge.py
index 604181214ad44..a66f52d45b761 100644
--- a/pandas/core/reshape/merge.py
+++ b/pandas/core/reshape/merge.py
@@ -1954,42 +1954,68 @@ def _validate_left_right_on(self, left_on, right_on):
     def _validate_validate_kwd(self, validate: str) -> None:
         # Check uniqueness of each
         if self.left_index:
-            left_unique = self.orig_left.index.is_unique
+            left_keys = self.orig_left.index
         else:
-            left_unique = MultiIndex.from_arrays(self.left_join_keys).is_unique
+            left_keys = MultiIndex.from_arrays(self.left_join_keys)
 
         if self.right_index:
-            right_unique = self.orig_right.index.is_unique
+            right_keys = self.orig_right.index
         else:
-            right_unique = MultiIndex.from_arrays(self.right_join_keys).is_unique
+            right_keys = MultiIndex.from_arrays(self.right_join_keys)
+
+        left_unique = left_keys.is_unique
+        right_unique = right_keys.is_unique
+
+        def sample_duplicates(keys, limit=10):
+            """Return up to 'limit' unique duplicate keys."""
+            dups = keys[keys.duplicated()]
+            if not len(dups):
+                return []
+            return list(dups.unique()[:limit])
 
         # Check data integrity
         if validate in ["one_to_one", "1:1"]:
             if not left_unique and not right_unique:
+                left_sample = sample_duplicates(left_keys, limit=5)
+                right_sample = sample_duplicates(right_keys, limit=5)
+
                 raise MergeError(
                     "Merge keys are not unique in either left "
-                    "or right dataset; not a one-to-one merge"
+                    "or right dataset; not a one-to-one merge. "
+                    f"Offending keys in left dataset (sample): {left_sample} "
+                    f"Offending keys in right dataset (sample): {right_sample} "
                 )
             if not left_unique:
+                sample = sample_duplicates(left_keys)
                 raise MergeError(
-                    "Merge keys are not unique in left dataset; not a one-to-one merge"
+                    "Merge keys are not unique in left dataset; "
+                    "not a one-to-one merge. "
+                    f"Offending keys (sample): {sample}"
                 )
             if not right_unique:
+                sample = sample_duplicates(right_keys)
                 raise MergeError(
-                    "Merge keys are not unique in right dataset; not a one-to-one merge"
+                    "Merge keys are not unique in right dataset; "
+                    "not a one-to-one merge. "
+                    f"Offending keys (sample): {sample}"
                 )
 
         elif validate in ["one_to_many", "1:m"]:
             if not left_unique:
+                sample = sample_duplicates(left_keys)
                 raise MergeError(
-                    "Merge keys are not unique in left dataset; not a one-to-many merge"
+                    "Merge keys are not unique in left dataset; "
+                    "not a one-to-many merge. "
+                    f"Offending keys (sample): {sample}"
                 )
 
         elif validate in ["many_to_one", "m:1"]:
             if not right_unique:
+                sample = sample_duplicates(right_keys)
                 raise MergeError(
                     "Merge keys are not unique in right dataset; "
-                    "not a many-to-one merge"
+                    "not a many-to-one merge. "
+                    f"Offending keys (sample): {sample}"
                 )
 
         elif validate in ["many_to_many", "m:m"]:
diff --git a/pandas/tests/reshape/merge/test_merge.py b/pandas/tests/reshape/merge/test_merge.py
index c38ee32cb7226..e940aba9f4018 100644
--- a/pandas/tests/reshape/merge/test_merge.py
+++ b/pandas/tests/reshape/merge/test_merge.py
@@ -3121,3 +3121,9 @@ def test_merge_pyarrow_datetime_duplicates():
     )
     expected = expected.convert_dtypes(dtype_backend="pyarrow")
     tm.assert_frame_equal(result, expected)
+
+
+def test_merge_validate_one_to_one_offending_keys():
+    df = DataFrame({"a": [1, 1, 3], "b": [4, 5, 6]})
+    with pytest.raises(pd.errors.MergeError, match="Offending keys"):
+        df.merge(df, on="a", validate="one_to_one")