A facile way for the synthesis of nano-crystalline CaCu_2.90Zn_0.10Ti₄O₁₂ (CCZTO) using a solution combustion technique based on the glycine–nitrate process with inexpensive solid TiO₂ powder as the raw material is introduced in this manuscript, for the first time. The precursor powder was calcined between 200 °C and 850 °C for 3 h in air. Phase formation, crystalline nature, morphology and chemical purity of the fabricated CCZTO were investigated with TG/DTA, FT-IR, FT-Raman, XRD, SAED patterns, SEM, TEM, EDX and XPS analyses, respectively. The XRD results indicated that all sintered samples had a major CaCu₃Ti₄O₁₂ structure with some amount of CaTiO₃ and CuO. The bright-field TEM micrographs revealed that the particle size was in the range of 15–50 nm, which was in good agreement with the average crystallite size obtained from XRD. SEM micrographs of the sintered CCZTO ceramics showed the average grain sizes were in the range of 800 nm–7 μm. EDX and XPS studies confirmed the stoichiometry and purity of the ceramics. The nature of the relaxation behavior of the ceramics was rationalized using impedance and modulus spectroscopy. The activation energies calculated from the grain-boundary relaxation time constant were found to be in the range of 0.79–0.52 eV, which confirmed the Maxwell–Wagner type of relaxation present in the ceramic. Our inexpensive novel solution chemistry based method for CCZTO_16h gives a high dielectric constant (799) and low dielectric loss (0.091) at 100 Hz at room temperature, which has potential significance for cost-effective technological applications in microelectronic devices.