diff --git a/src/requests/adapters.py b/src/requests/adapters.py
index 40fe8a6d5a..b5d0f0a65b 100644
--- a/src/requests/adapters.py
+++ b/src/requests/adapters.py
@@ -742,6 +742,17 @@ def send(
                 raise ReadTimeout(e, request=request)
             elif isinstance(e, _InvalidHeader):
                 raise InvalidHeader(e, request=request)
+            elif isinstance(e, LocationValueError):
+                # urllib3 may raise LocationParseError (subclass of
+                # LocationValueError) from inside `create_connection` when the
+                # hostname has labels that fail validation (e.g. a label longer
+                # than 63 characters). prepare_url catches this at parse time,
+                # but the same exception can also be raised later from the
+                # socket layer where it would otherwise bubble up to the caller
+                # as a urllib3 exception. Wrap it in InvalidURL so users see a
+                # requests-native exception, matching the behaviour of
+                # get_connection_with_tls_context above. See GH #5744.
+                raise InvalidURL(e, request=request)
             else:
                 raise
 
diff --git a/tests/test_requests.py b/tests/test_requests.py
index 571535fe79..c00f24c81f 100644
--- a/tests/test_requests.py
+++ b/tests/test_requests.py
@@ -588,6 +588,13 @@ def test_basicauth_encodes_byte_strings(self):
             ("http://localhost:1", ConnectionError),
             # Inputting a URL that cannot be parsed should raise an InvalidURL error
             ("http://fe80::5054:ff:fe5a:fc0", InvalidURL),
+            # A DNS label longer than 63 chars survives prepare_url but is
+            # rejected by urllib3 inside create_connection. Should surface as
+            # InvalidURL, not as a raw urllib3.LocationParseError. GH #5744.
+            (
+                "http://" + ("a" * 64) + ".example.com",
+                InvalidURL,
+            ),
         ),
     )
     def test_errors(self, url, exception):