A neworganocatalyticstrategy for the synthesis of enantioenriched aza‐Baylis–Hillman type products via a frustrated vinylogous reaction is presented. This process proceeds under mild conditions with good yields, completed Z/E selectivity and excellent enantioselectivities. Moreover, easy derivatizations of the final products led to important building blocks of organic synthesis such as 1,3‐aminoalcohols