Your subselect in the WHERE clause is making comparisons on the aggregate COUNT(u.ULN) value, and therefore really belongs in a HAVING clause. It should be significantly more performant there, because the subselect would be evaluated for every row returned by the outer query while the HAVING filter will only be applied once for the entire aggregate query.
SELECT
l.user_id,
u.ID, u.ULN,
count(u.ULN) As ULN_count
FROM
table_Learning l
LEFT JOIN table_users u
ON l.ULN = u.ULN
WHERE l.user_id is null
GROUP BY u.ULN
-- The aggregate can be compared & filtered in HAVING
-- which is applied just once for the whole query
-- and you can use the alias for comparison
HAVING ULN_count < 2
Without seeing your sample data, it is possible that MySQL's default GROUP BY behavior may cause you some grief. All columns in the SELECT which are not part of an aggregate like COUNT(),SUM(),MAX() should also be included in the GROUP BY, in particular if you are joining multiple tables. In something other than a one-to-one relationship, MySQL may return indeterminate results for the ungrouped columns (l.user_id in this context).
GROUP BYbehavior because you have several columns inSELECTnot also included inGROUP BYand not aggregated. That will often cause indeterminate groupings, and results in a compile error in most RDBMS besides MySQL.WHERE, it seems like that entire thing may be eliminated fromWHEREand replaced withHAVING COUNT(u.ULN) < 2