An NHC-catalyzed cascade cycloaddition reaction is developed for quick access to structurally sophisticated tetrahydrochromeno[4,3-b]pyrrole derivatives. A sterically congested tetrasubstituted chirality carbon center is formed during the cyclization process. All the α-, β-, and carbonyl carbons of the enal substrates are functionalized in chemo- and stereoselective fashion. The multicyclic chromeno[4,3-b]pyrrole products are generally afforded in good yields with excellent enantio- and diastereoselectivities. Heavily substituted pyrroline derivatives can be afforded from the chiral products through simple protocols.