Structure, defects, non-ohmic behavior and dielectric properties of CaCu3Ti4O12 (CCTO) ceramics with furnace-cooled and water-quenched methods have been systemically investigated. Cooling methods make an influence on reoxidation process and cause changes of electric properties in grains and at grain boundaries. SEM-EDS provides detailed imaging information about Cu-rich phase on the fracture of CCTO ceramics which is explained by the reoxidation reaction during cooling. Morphologies of the water-quenched sample show very small grains floating in bigger grains; whereas they reveal that many grains are surrounded by an exfoliated sheet of Cu-rich phases in the furnace-cooled sample. The polaron relaxation associated with Ti3+ ions and oxygen vacancies occurs at low temperatures, and more Ti3+ ions are remained in the water-quenched sample. The Schottky barrier height (I-V, non-ohmic behavior) associated with the reoxidation of grain boundaries can be modified by cooling method. (C) 2013 Elsevier B.V. All rights reserved.