Bismuth-ion doped Cu(In,Ga)Se-2 (CIGS) solar cells were fabricated via sputtering technique. The influence of bismuth-ion doping on structural and photovoltaic characteristics of the fabricated CIGS films were explored in details. With doping of bismuth ions, the grain sizes of CIGS layers were enhanced appreciably due to liquid-phase sintering with the yielded intermediate compound. The secondary ion mass spectroscopy profile results indicated that the diffusion of bismuth ions into CIGS layers promoted dissemination of gallium species from the back contacts to the surface of CIGS layers. According to Hall measurement analysis, the carrier concentration in CIGS films was enhanced significantly with the doping of bismuth ions in the prepared films. The conversion efficiency of the bismuth-ion doped samples was increased approximately 10% in comparison with undoped samples due to the elevated gallium-ion diffusion and grain growth. Various photovoltaic parameters including saturated current and diode factors of the prepared doped CIGS solar cells were decreased owing to the inhibition of electron-hole recombination. This investigation demonstrated the improved photovoltaic performance and the structural characteristics of fabricated CIGS films after the doping of bismuth ions.