A light-emitting organic solar cell (LE-OSC) with electroluminescence (EL) and photovoltaic (PV) properties is successfully fabricated by connecting the EL and PV units using a MoO₃:Al co-evaporation interfacial layer, which has suitable work function and good transmittance. PV and EL units are fabricated based on poly(3-hexylthiophene) (P3HT)-indene-C60 bisadduct (IC60BA) blends, and 4,4′-bis (N-carbazolyl) biphenyl-factris (2-phenylpyridine) iridium (Ir(ppy)3), respectively. The work function and the transmittance of the MoO₃:Al co-evaporation are measured and adjusted by the ultraviolet photoelectron spectroscopy and the optical spectrophotometer to obtain the better bi-functional device performance. The forward- and reverse-biased current density-voltage characteristics in dark and under illumination are evaluated to better understand the operational mechanism of the LE-OSCs. A maximum luminance of 1550 cd/m² under forward bias and a power conversion efficiency of 0.24% under illumination (100 mW/cm²) are achieved in optimized LE-OSCs. The proposed device structure is expected to provide valuable information in the film conditions for understanding the polymer blends internal conditions and meliorating the film qualities.