Counterion-mediated asymmetric catalysis is an effective strategy in organocatalysis or metal-based catalysis. We have initiated an investigation of this strategy in the aza-Morita-Baylis-Hillman (MBH) reaction to address the rate and substrate scope issue. Trifunctional organocatalysts, each containing a Lewis base, a Brønsted base, and a Brønsted acid, have been designed and developed to catalyze this reaction with positive cooperativity. The Brønsted base acts as the switch point to the counterion catalytic pathway, in response to the addition of an external strong Brønsted acid, to furnish fast reaction rates with good enantioselectivity at ambient temperature, with the counteranion of the Brønsted acid additive controlling the sense of the asymmetric induction. Further generations of this new class of organocatalysts have shown improved enantioselective rates and substrate scope in the aza-MBH reaction. Asymmetric multidentate organocatalysis, with positive cooperativity and regulation, may lead to new approaches to enzyme mimicking catalysis with proficiency.