A novel and efficient approach for the straightforward synthesis of biologically significant acenaphtho[1,2-b]quinoline derivatives in good yields utilizing CuI as a catalyst with a broad array of substrates has been developed. The strategy features as a CuI-catalyzed cascade reaction involving the formation of two new C–C bonds and one new C–N bond with high atom economy. A proposed mechanism for the reaction is described. A novel and efficient approach for the straightforward synthesis of biologically significant acenaphtho [1,2-b] quinoline derivatives in good yields utilizing CuI as a catalyst with a broad array of substrates has been developed. The strategy features as a CuI-catalyzed cascade reaction involving the formation of two new C-C bonds and one new C-N bond with high atom economy. A proposed mechanism for the reaction is described.