Y-doped BaZrO3 proton conductor has been extensively studied due to its outstanding chemical stability. However, the high sintering temperature has limited its practical application. To enhance the sintering activity of BaZrO3, we co-doped Y-BaZrO3 with Pr3+ and Ni2+, and investigated its microscopic morphology and electrochemical properties. The introduction of Ni forms a solid solution with the sample, while Pr3+ doping increases the grain size, a critical factor for the densification process. XPS, Raman and EPR results reveal that a small amount of Pr3+ doping significantly raises the concentration of oxygen vacancies in the materials. This increase promotes proton incorporation by accelerating the dissociation and adsorption of water, thereby facilitating the proton conduction. However, it’s important to note that excessive Pr3+ doping leads to a high concentration of oxygen vacancies, which triggers a defect association reaction. Consequently, this results in a slight decrease in conductivity at low temperatures. On the other hand, as the temperature increases, the hydrogen permeability of the membrane increases also rises. Moreover, the hydrogen permeability of BaZr0.66Y0.2Pr0.1Ni0.04O3-δ is found to be higher than that of BaZr0.71Y0.2Pr0.05Ni0.04O3-δ, with the former reaching 2.60×10-8 mol·cm-2·s-1 at 1 173 K. Notably, these membranes exhibit remarkable in CO2-containing atmosphere indicating excellent resistance to CO2.