diff --git a/changelog.d/18342.bugfix b/changelog.d/18342.bugfix
new file mode 100644
index 000000000..6fa2fa679
--- /dev/null
+++ b/changelog.d/18342.bugfix
@@ -0,0 +1 @@
+Fix `ExternalIDReuse` exception after migrating to MAS on workers with a high traffic.
diff --git a/synapse/storage/databases/main/registration.py b/synapse/storage/databases/main/registration.py
index eadbf4901..c43f31353 100644
--- a/synapse/storage/databases/main/registration.py
+++ b/synapse/storage/databases/main/registration.py
@@ -763,16 +763,33 @@ class RegistrationWorkerStore(CacheInvalidationWorkerStore):
             txn, self.get_user_by_external_id, (auth_provider, external_id)
         )
 
-        self.db_pool.simple_insert_txn(
+        # This INSERT ... ON CONFLICT DO NOTHING statement will cause a
+        # 'could not serialize access due to concurrent update'
+        # if the row is added concurrently by another transaction.
+        # This is exactly what we want, as it makes the transaction get retried
+        # in a new snapshot where we can check for a genuine conflict.
+        was_inserted = self.db_pool.simple_upsert_txn(
             txn,
             table="user_external_ids",
-            values={
-                "auth_provider": auth_provider,
-                "external_id": external_id,
-                "user_id": user_id,
-            },
+            keyvalues={"auth_provider": auth_provider, "external_id": external_id},
+            values={},
+            insertion_values={"user_id": user_id},
         )
 
+        if not was_inserted:
+            existing_id = self.db_pool.simple_select_one_onecol_txn(
+                txn,
+                table="user_external_ids",
+                keyvalues={"auth_provider": auth_provider, "user_id": user_id},
+                retcol="external_id",
+                allow_none=True,
+            )
+
+            if existing_id != external_id:
+                raise ExternalIDReuseException(
+                    f"{user_id!r} has external id {existing_id!r} for {auth_provider} but trying to add {external_id!r}"
+                )
+
     async def remove_user_external_id(
         self, auth_provider: str, external_id: str, user_id: str
     ) -> None: