Herein, V2O5 thin films were deposited through O2-reactive radio frequency (RF) magnetron sputtering using a metallic vanadium arget without external heating on a glass substrate. The influence of the RF power and O2 content on phase formation was investigated, and the percentage of the phase volume was related to the electrical and optical properties of the films. These films were composed of a mixture of α and β phases of V2O5, and the coexistence of monoclinic (βм) and tetragonal (βт) symmetries of the β-phase structure was observed. The phase of the film deposited at 100 W RF power with 10% O2 was βт. Increasing the RF power to 150 W led to the development of the βм phase in the film. At 200 W, the obtained film was a mixture of βм- and α-V2O5 phases, and the film produced with an O2 content of more than 10% was a mixture of three phases: βт-, βм-, and α-V2O5. Further increase in the O2 content decreased the βм-phase volume but increased the βт-phase volume. The electrical resistivity and optical properties depended on the phase volume. Furthermore, the relationship between the phase volume and film properties is presented.