The asymmetric dearomative formal [4 + 2] cycloaddition reaction of activated N,4-dialkylpyridinium salts and acyclic α,β-unsaturated ketones was developed by the cascade iminium ion-enamine catalysis of a cinchona-derived amine. A spectrum of valuable azaspiro[5.5]undecane architectures was efficiently constructed with high to excellent diastereoselectivity and enantioselectivity.