An eco‐friendly, highly‐efficient, atom‐economical three‐component cascade reaction of acenaphthenequinone (8), β‐nitroolefins (9) and α‐amino acid (10) in MeOH/H2O is developed for the synthesis of novel functionalized polycyclic N‐fused‐pyrrolidine derivatives (11). All products are obtained by filtration in the absence of column chromatography and recrystallization. Due to its operational simplicity, this green and chemically sustainable reaction can be easily applied toward the design and synthesis of target molecules for the discovery of novel biologically active compounds.