In the present work, structural, dielectric and electrical properties of lead zirconate titanate and CaCu3Ti4O12 ceramic composite with composition (1-x)Pb(Zr0.65Ti0.35)O3 - xCaCu3Ti4O12 (where x = 0, 0.20, 0.40 and 0.60) has been reported. The sample was prepared by employing a high-temperature solid-state reaction technique. X-ray diffraction studies confirm the formation of pure phase for x = 0.00 concentration and composite phases for the x = 0.40, 0.60 compositions. Doublet of diffraction peaks suggests structural change for x = 0.20 composition. Scanning electron micrographs show a uniform grain distribution and the grain size and shape modified upon CaCu3Ti4O12 addition. Dielectric measurement demonstrates a decrease in the dielectric constant with increase in CaCu3Ti4O12 percentage. The prepared ceramic composites have high dielectric constant and low dielectric loss. The temperature dependence of the ac conductivity indicated that the conduction process is due to singly ionized (in ferroelectric region) and doubly ionized (in paraelectric region).