Novel dielectrics with electrostatic energy storage capabilities attracted significant attention in recent years for high-energy storage applications due to their high-power density. The structural, electrical, and dielectric properties play a pivotal role in attaining high power densities in dielectric ceramics. Here, the authors presented the influence of CaTiO3 on the structural, electrical, and dielectric properties of BiFeO3-CaTiO3 (BFO-CTO) lead-free ceramics. (BFO)(1−x)–(CTO)x (x = 0, 0.1, 0.3, and 0.5 and 1) ceramics were fabricated from calcined powders of BFO and CTO using the microwave sintering technique. Due to the partial substitution of Ca2+ and Ti4+ into the A and B sites (of Bi3+ and Fe3+, respectively) structural phase transformation occurred from rhombohedral to orthorhombic crystal structure for x ≥ 0.3. As the CTO concentration is increased, the resistivity of BFO-CTO samples is enhanced by two orders of magnitude, from 2.21 × 103 Ω cm (x = 0) to 8.80 × 105 Ω cm (x = 0.5). The leakage current density was reduced by two orders of magnitude, from ~ 2.60 × 10–1 A cm−2 (x = 0) to ~ 2.50 × 10–3 A cm−2 (x = 0.5). The improved resistivity, reduced leakage current and enhanced dielectric properties make lead-free BFO-CTO dielectrics as an excellent alternative to existing energy storage systems.