ZrF4-based binary glass film is synthesized for the first time by plasma-enhanced chemical vapor deposition (PCVD). The optical transmission spectrum is measured and the effects of oxygen doping on the glass forming ability are clarified. No absorption band caused by OH or other impurities is observed in the near IR region. Weak absorption bands attributed to defect centers are observed in the UV to visible region. The glass forming region in the ZrF4-BaF2 system is significantly improved by oxygen doping. Oxygen ions are distributed homogeneously in the fluoride glass film by PCVD and improve its stability against crystallization.