2ZrO2·P2O5 powder, which is not synthesized by solid reaction method, was successfully synthesized through PVA solution method. In this process, the firing temperature and the PVA content strongly affected the crystallization behavior and final particle size. A stable α-phase 2ZrO2·P2O5 was synthesized at a firing temperature of 1200 °C and holding time of 4 h. β-phase 2ZrO2·P2O5 was observed, with un-reacted ZrO2 phases, for firing temperatures lower than 1200 °C. In terms of the PVA content effect, the powder prepared with a PVA mixing ratio of 12:1 showed stable α-phase 2ZrO2·P2O5; however, the β-phase was found to co-exist at relatively higher PVA content. The synthesized α-phase 2ZrO2·P2O5 powder showed an average particle size of 100~250 nm and an average thermal expansion coefficient of -2.5 × 10-6/°C in the range of room temp. ~800 °C.