We fabricated doping-free intrinsic amorphous silicon (i-a-Si) thin-film solar cells having a structure of glass/SnO2/MoO3/i-a-Si/LiF/Al. The short-circuit current density of the cell markedly increased while the open-circuit voltage and fill factor were low due to a lower work-function of the MoO3 than that of a conventional amorphous silicon carbide film. To solve these drawbacks, we UV-treated on the MoO3 layer, obtaining a greatly enhanced conversion efficiency of 6.42%.