CaCu3Ti4O12 (CCTO) was prepared by a conventional synthesis (CS) and through reaction sintering, in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of CCTO have been studied by XRD, FE-SEM, EDS, AFM, and impedance spectroscopy to correlate structure, microstructure, and electrical properties. Samples prepared by reactive sintering show very similar dielectric behavior to those prepared by CS. Therefore, it is possible to prepare CCTO by means of a single-step processing method