A nickel(II)-catalyzed unexpected [3 + 2] cycloaddition/[3,3]-rearrangement cascade reaction was developed for the preparation of various polysubstituted 1-pyrroline-tethered quinazolinones containing three contiguous stereocenters in moderate to good yields with high diastereoselectivity from N-vinyl cinnamaldehyde nitrones and 2-alkynyl quinazolinones. Polysubstituted pyrrolizine-tethered quinazolinones were obtained in good yields when N-vinyl cinnamaldehyde nitrones were replaced by N-vinyl chalcone nitrones. The present method features a broad substrate scope, high [3,3]-rearrangement selectivity and diastereoselectivity, and two substituent bifurcated types of N-heterocycles.