Herein, we have synthesized four indolo[2,3-b]quinoxalin-2-yl)(phenyl)methanone derivatives by cyclocondensation. The photophysical studies of dyes in various solvents and neat solid film exhibit typical electronic spectra with inbuilt intramolecular charge transfer (ICT) (?max: 397–490 nm) confirming donor–acceptor architecture. Herein, dyes fluoresce in the blue-orange region (?Emax: 435–614) on excitation at their ICT maxima in toluene, ethyl acetate, chloroform, DMSO, and neat solid film. Two dyes, which exhibit good emission intensity in all mediums, were studied for aggregation-induced emission (AIE) effect. Electrochemical studies indicate the dyes possess relatively low lying LUMO (- 3.65 to - 3.98 eV) comparable to reported n-type/electron-transporting materials. The HOMO and LUMO energy levels were evaluated by DFT and TD-DFT calculations. TGA analysis shows the dyes exhibit good thermal stability. The characteristic optoelectronic properties and thermal stability signify these dyes are potential candidates for their application in optoelectronics.