CaCu3Ti4O12 (CCTO) is a perovskite-type material characterized by a high dielectric constant, which remains almost constant over a wide range of frequencies and temperatures. These characteristics make this material promising for industrial applications, in particular for electronic devices. Although so-gel procedures are well established in the synthesis of complex oxides, there are few studies reporting their use for the synthesis of CCTO. Once sol-gel techniques allow to obtain pure phase products and to control precisely their stoichiometry, they are a good alternative way for the preparation of perovskite-type oxides, namely CCTO. In our work, single phase CCTO has been prepared for the first time, as far as we know, by ethylenediaminetetraacetic acid (EDTA) gel combustion synthesis process. Nanocrystalline CCTO powders obtained after calcination were characterized by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). Dielectric spectroscopy measurements were performed on the sintered pellets, in the frequency range from 40 Hz to 30 MHz, at several temperatures. A single relaxation time, described by the equation of Debye, cannot be used to explain the observed dielectric relaxation. We have analysed the data with the Cole-Cole model, which adjusts correctly the data. The calculated relaxation parameters were correlated with morphologic and structural properties. (C) 2010 Elsevier B.V. All rights reserved.