Polyenals and polyenones are simple chemical compounds which can be constructed into large and complex structures by virtue of aminocatalysis. In the past eight years, new aminocatalytic activation modes based on trienamine, cross‐trienamine, tetraenamine, iminium ion, and vinylogous iminium ion intermediates have attracted great attention in the field of asymmetric synthesis. Key to the increasing focus is their inherent ability to allow functionalization of remote sites with excellent stereoselectivities. Moreover, methodologies involving one‐pot, cascade or multicomponent strategies have been developed through the combination of these new activation modes with classical activation modes. In the course of expanding the applicability of organocatalysis, polyenals and polyenones have been introduced as simple and novel substrates, which have enabled the discovery of new concepts for the synthesis of many diverse and complex privileged structures.