diff --git a/crates/polars-plan/src/plans/conversion/join.rs b/crates/polars-plan/src/plans/conversion/join.rs
index 0cd7c1563719..6c3e28bb6c7a 100644
--- a/crates/polars-plan/src/plans/conversion/join.rs
+++ b/crates/polars-plan/src/plans/conversion/join.rs
@@ -130,6 +130,17 @@ fn resolve_join_where(
 ) -> PolarsResult<Node> {
     check_join_keys(&predicates)?;
 
+    for e in &predicates {
+        let no_binary_comparisons = e
+            .into_iter()
+            .filter(|e| match e {
+                Expr::BinaryExpr { op, .. } => op.is_comparison(),
+                _ => false,
+            })
+            .count();
+        polars_ensure!(no_binary_comparisons == 1, InvalidOperation: "only 1 binary comparison allowed as join condition")
+    }
+
     let owned = |e: Arc<Expr>| (*e).clone();
 
     // Partition to:
diff --git a/py-polars/polars/dataframe/frame.py b/py-polars/polars/dataframe/frame.py
index f0d2d1abe2e4..bca6762cccdd 100644
--- a/py-polars/polars/dataframe/frame.py
+++ b/py-polars/polars/dataframe/frame.py
@@ -7095,6 +7095,10 @@ def join_where(
         """
         Perform a join based on one or multiple equality predicates.
 
+        .. warning::
+            This functionality is experimental. It may be
+            changed at any point without it being considered a breaking change.
+
         A row from this table may be included in zero or multiple rows in the result,
         and the relative order of rows may differ between the input and output tables.
 
@@ -7111,6 +7115,13 @@ def join_where(
         suffix
             Suffix to append to columns with a duplicate name.
 
+        Notes
+        -----
+        This method is strict about its equality expressions.
+        Only 1 equality expression is allowed per predicate, where
+        the lhs `pl.col` refers to the left table in the join, and the
+        rhs `pl.col` refers to the right table.
+
         Examples
         --------
         >>> east = pl.DataFrame(
diff --git a/py-polars/polars/lazyframe/frame.py b/py-polars/polars/lazyframe/frame.py
index d326e5e15abc..44978528e272 100644
--- a/py-polars/polars/lazyframe/frame.py
+++ b/py-polars/polars/lazyframe/frame.py
@@ -4574,6 +4574,10 @@ def join_where(
         A row from this table may be included in zero or multiple rows in the result,
         and the relative order of rows may differ between the input and output tables.
 
+        .. warning::
+            This functionality is experimental. It may be
+            changed at any point without it being considered a breaking change.
+
         Parameters
         ----------
         other
@@ -4587,6 +4591,13 @@ def join_where(
         suffix
             Suffix to append to columns with a duplicate name.
 
+        Notes
+        -----
+        This method is strict about its equality expressions.
+        Only 1 equality expression is allowed per predicate, where
+        the lhs `pl.col` refers to the left table in the join, and the
+        rhs `pl.col` refers to the right table.
+
         Examples
         --------
         >>> east = pl.LazyFrame(
diff --git a/py-polars/tests/unit/operations/test_inequality_join.py b/py-polars/tests/unit/operations/test_inequality_join.py
index e639de2ac62e..7b3ddb279fec 100644
--- a/py-polars/tests/unit/operations/test_inequality_join.py
+++ b/py-polars/tests/unit/operations/test_inequality_join.py
@@ -447,3 +447,11 @@ def test_raise_on_suffixed_predicate_18604() -> None:
     df = pl.DataFrame({"id": [1, 2]})
     with pytest.raises(pl.exceptions.ColumnNotFoundError):
         df.join_where(df, pl.col("id") >= pl.col("id_right"))
+
+
+def test_raise_on_multiple_binary_comparisons() -> None:
+    df = pl.DataFrame({"id": [1, 2]})
+    with pytest.raises(pl.exceptions.InvalidOperationError):
+        df.join_where(
+            df, (pl.col("id") < pl.col("id")) & (pl.col("id") >= pl.col("id"))
+        )