A 2‐oxopyrimidinium salt was immobilized onto a polystyrene‐derived polymer to generate a heterogeneous catalyst that effectively promoted the asymmetric Michael addition of glycine‐derived imines to α,β‐unsaturated ketones. The reactions proceeded smoothly to afford the desired adducts, (S)‐tert‐butyl 2‐[(diarylmethylidene)amino]‐5‐oxoalkanoates, in high yields and with high enantioselectivities (up to 92% ee). The polymer catalyst could be recovered and reused at least five times without significant loss of activity or selectivity.