[mysql] How to delete a certain row from mysql table with same column values?

You need to specify the number of rows which should be deleted. In your case (and I assume that you only want to keep one) this can be done like this:

DELETE FROM your_table WHERE id_users=1 AND id_product=2
LIMIT (SELECT COUNT(*)-1 FROM your_table WHERE id_users=1 AND id_product=2)