A thermodynamic-promoting diastereoselective synthesis of dispirooxindole-pyrrolizines was developed by a five-component reaction with a dual 1,3-dipolar cycloadditions process of non-stabilized azomethine ylides that includes the decarboxylation of glycine and αCH functionalization of generated pyrrolidines in situ. This process is a solid and versatile strategy for rapidly assembling fused pyrrolizines with two spirooxindoles bearing seven stereocenters. Homogeneous Brønsted acid catalysis and benign solvent in one-step reaction can be used to promote the green process, with by-products of CO2 and H2O, and potentiating environmental tolerance.