The Ba1-xCaxZryTi1-yO3 (BCZT; x = 0.18, y = 0.08; x = 0.15, y = 0.10; x = 0.12, y = 0.12; x = 0.09, y = 0.14; both x and y are in mol. %) piezoceramics were prepared by solid-state reaction method and investigated their energy storage and harvesting responses. The composition x = 0.15, y = 0.10 ( i.e. BCZT-2) reveals the morphotropic phase boundary (MPB) near room temperature with enhanced piezoelectric properties such as piezoelectric charge coefficient (d33) ∼ 380 pC/N, piezoelectric strain coefficient (d33*) ∼ 583.71 pm/V, piezoelectric voltage coefficient (g33) ∼ 14.09 ×10−3Vm/N, figure of merits (d33×g33) ∼ 5.35 ×10−12m2/N and the electromechanical coupling coefficient (kp) ∼ 0.291. The harvested peak-to-peak open circuit AC voltage is 30 V and the calculated current is in the range of 0.02–0.14 mA with varied load resistance and the maximum obtained power density is 13.38 μW/mm3 for BCZT-2 ceramics. The DC output signal of BCZT-2 ceramics successfully lit up the 'FCLNT' panel consisting of 53 red LEDs. At room temperature, BCZT ceramics have a recoverable energy storage density (Wrec) and storage efficiency (η) in the range between 506.46 and 257.49 mJ/cm3 and 50.53 – 64.93 % respectively. The composition x = 0.12, y = 0.12 (i.e. BCZT-3) revealed the highest energy storage efficiency (η) ∼ 64.93 % at room temperature. Nonetheless, the temperature-dependent (till its Curie temperature) maximum obtained Wrec of all BCZT ceramics is found in the range between 238.41 and 446.49 mJ/cm3 with an η of 66.98–79.67 %. Thus, compositionally tuned BCZT ceramics exhibit considerable piezoelectric properties, including energy storage and harvesting capabilities.