Reported herein is a sustainable approach for a regioselective, Rh(III)-catalyzed C(7)-H alkylation of 8-aminoquinolines via metal carbene migratory insertion. This transformation displays a high functional group tolerance and exquisite site selectivity to afford the C-7 alkylated products. These products are derivatized to afford π-extended angular pyrroloquinolines, one of which (4h) shows white-light emission (WLE) with CIE coordinates (0.26, 0.34). An excellent cell viability and in vivo cellular imaging substantiate the nontoxic nature of these compounds.