Tailoring the electronic, optical, and transport properties of low-dimensional semiconductor materials is essential to improve the lightconversion efficiency of thin-film solar cell materials. Here, using first-principles calculations and non-equilibrium Green functions, we investigate the enhancement of optoelectronic and transport properties of armchair graphene nanoribbons (AGNRs) upon adsorption of cadmium selenide clusters. Upon adsorption of a CdSe diatomic molecule on an AGNR, the most energetically favorable configuration is the cadmium end sitting on top of a carbon atom. The corresponding electronic bandgap reduces ∼5 times with respect to that of the pristine system, thanks to the formation of a polaron state formed by the p-orbital of the selenide atom. Upon adsorption of CdSe cyclohexane molecules, the bandgap of this system slightly shrinks by 0.121 eV with respect to the pristine system. The charge accumulation induced by these clusters significantly enhances the absorption coefficient of the adsorbed systems, resulting in a red shift of the optical spectra toward the infrared region. More interestingly, by solving the Bethe–Salpeter equations with the Tamm–Dancoff approximation, we provide a direct link between the first-principles optical prediction and experimental observations. In addition, the electron transfer from these molecules to the hosted systems increases the transmission spectra in the vicinity of the Fermi level, leading to a remarkable electronic current passing through these scattering regions. These results highlight the role of cadmium selenide clusters in enhancing the light-to-energy conversion efficiency of next-generation solar cell devices.