Vanadium dioxide (VO2) thin films with pure Monoclinic phase could be transformed from B-phase by inserting TiO2 buffer layers on transparent amorphous glass substrates at the low temperature of 400 °C. This crystalline transformation might be ascribed to oxygen-deficient environment induced by the TiO2 buffer layer and the template effect of TiO2 layer for M-VO2 phase. The simplicity in phase regulation of the present method and the superior optical and electrical properties of the films may allow its wide applications in thermo-opto-electro sensing devices.