An efficient and straightforward approach for the synthesis of trifluoromethyl-decorated benzo[de][1,8]naphthyridines has been achieved via the Rh(III)-catalyzed dual C-H activation and cascade annulation of benzimidates and CF3-imidoyl sulfoxonium ylides. The novel transformation involves the formation of four new chemical bonds along with the release of two molecules of dimethyl sulfoxide (DMSO) and one molecule each of ethanol and amine. The optoelectronic properties of the obtained fused aromatic products have been investigated by recording the UV-vis absorption and emission spectra.