Non-ohmic and dielectric properties of Ca2Cu2Ti4O12 (CaCu3Ti4O12/CaTiO3 composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ɛ′ (tanδ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050°C for 10h exhibits the high ɛ′ of 2530 with weak frequency dependence below 1MHz, the low tanδ less than 0.05 in the frequency range of 160Hz–177kHz, and the little temperature coefficient, i.e., |Δɛ′|≤15% in the temperature range from −55 to 85°C. These results indicate that the CaCu3Ti4O12/CaTiO3 composite system prepared by PP method is a promising high-ɛ′ material for practical capacitor application