A new hybrid-type squaramide-fused amino alcohol organocatalyst containing both a Brønsted-basic site and a hydrogen-bonding site showed high catalytic activity in the enantioselective Diels–Alderreactions of 3-hydroxy-2-pyridones with maleimides to afford the chiral 4-hydroxyisoquinuclidines with high regio- and stereoselectivity.