Rare earth ions doped ferroelectric ceramics have attracted much attention because rare earth ions can effectively regulate the ferroelectric and energy storage properties of ceramics. Herein, Ba1-xCaxTi1-yHfyO3 ceramics modified with Ca2+ and Hf4+ are prepared, and the effects of different Ca2+ and Hf4+ concentrations on the crystal structure, microstructure and electrical properties of Ba1-xCaxTi1-yHfyO3 ceramics are investigated. Through the analysis on the ceramic structure and electrical properties, Ba0.96Ca0.04Ti0.85Hf0.15O3 (BCTH) ceramic shows excellent comprehensive performance. Using BCTH ceramic as matrix material, the influences of different Pr3+ concentrations on the structure and electrical properties of the BCTH: x%Pr3+ ceramics are studied. Energy storage efficiency (η) gradually increases with the increase of Pr3+ concentration, while the energy storage density (Wd) shows a trend of first increasing and then decreasing, reaching the maximum value for x = 0.6 (Wd = 0.338 J/cm3, η = 87.86 %), which was higher than that of pure BCTH ceramics (Wd = 0.212 J/cm3, η = 78.05 %) increased by 59.43 % and 12.57 %, respectively. All the samples show good stability of energy storage temperature and frequency. After Pr3+ doping, the Curie transition temperature of the ceramics first increas and then decreases, and show a wider transition peak, indicating that the transition from ferroelectrics to relaxation ferroelectrics occurres. The excellent electrical properties of BCTH: x%Pr3+ ceramics indicate their potential application value in the field of electricity.