The effect of La³⁺, Mn²⁺ and Ni²⁺ doped calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO), at higher concentrations (CR1 and CR2 with 5 mol% and 10 mol%, respectively), has been examined by semi-wet route at relatively lower temperature. This semi-wet route employs citrate–nitrate gel chemical method using TiO₂ solid powders. X-ray diffraction (XRD) analysis confirms the formation of single phase in the doped samples sintered at 900 ℃ for 8 h. Scanning electron micrographs (SEM) show that the average grain size for CR2 is larger than that of CR1 composition. The energy dispersive X-ray spectroscopy (EDX) is used to study the percentage compositions of different ions present in both ceramics. Dielectric constant (ε_r) and dielectric loss (tanδ) values of CR1 are comparatively higher than those of CR2 ceramic at all measured frequencies and temperatures. The nature of temperature-dependent relaxation behavior of the ceramics is also studied by impedance, modulus spectroscopic analysis and confirms Maxwell–Wagner relaxation.