Herein, we present a strategy for the synthesis of pyrrole alkaloid derivatives through a tandem C-N, C-C coupling reaction employing 2-pyrrole formaldehyde and proline as starting materials. This cyclization protocol is successfully applied to polarity-controlled site-selective and stereoselective C(sp(3))-H hydrocarboxylation of proline derivatives, allowing for a remarkably streamlined synthesis of pyrrole alkaloid derivatives which have shown promising biological activities.