The step-economical synthesis of pyrrole derivatives has posed a challenge in the field of N-heterocyclic chemistry. A novel photocascade catalytic radical SN2'-type reaction/radical addition/annulation sequence of MBH acetates provides a straightforward route to pyrrole derivatives by forming new C-C, C-N, and C═C bonds in one pot, using N-arylglycines as the α-arylaminomethyl radical precursors for double insertion.