The relationship between dielectric performance and sample thickness in CaCu3Ti4O12 ceramics was investigated. The geometric dimensional effect, observed in gradually grinded CaCu3Ti4O12 samples, is referred to as the responsible parameter for the change in breakdown field and nonlinear coefficient with the variation in the thickness. An inflection point behavior of the breakdown electric field, analogous to ZnO based varistor, can be observed with reduced thickness. When the thickness was reduced from 2.2 mm to 0.45 mm, the low-frequency (<100 Hz) dielectric permittivity and dielectric loss was increased while high frequency dielectric relaxation can be barely affected. Impedance spectroscopy results show that the grain resistance remained as similar to 40 Omega cm, while grain boundary resistance decrease sharply from 79 M Omega cm to 14 M Omega cm. Scanning electron micrographs illustrate that there exists great difference between microstructure of surface area and interior area along thickness direction, which can be possibly caused by heterogeneous diffusion of oxygen and liquid phase sintering of ceramics. It was proposed that grain boundary play a key role in the dimensional effect, which can also be verified by the results of as-sintered CaCu3Ti4O12 samples with varied thickness. (C) 2015 Elsevier B.V. All rights reserved.