Hydrogen energy is one of the most developing areas of clean energy due to various advantages of hydrogen compared to traditional fossil fuels. One of hydrogen energy electrochemical devices is proton-conducting solid oxide fuel cells. The obtaining of novel highly proton conductive materials is relevant. Nonmetal doping strategy to improve the protonic conductivity in perovskite-related materials is understudied. The phosphorous-doped perovskite CaZr0.95P0.05O3.025 was obtained for the first time. The possibility for water uptake was proved by thermogravimetry and mass-spectrometry investigations. It was shown that phosphorous doping led to increase in the conductivity values up to 500 times. The composition CaZr0.95P0.05O3.025 demonstrates nearly pure proton transport below 600 °C under wet air. The proton conductivity values are 3.3·10−6 S/cm at 670 °C and 7.6·10−7·S/cm at 500 °C. The nonmetal doping strategy is prospective way to enhance electrical conductivity of proton conductors with perovskite structure.