A high-temperature solid-state reaction technique was used to prepare polycrystalline samples of Pb(Zr 0.65− x Ce x Ti 0.35 )O 3 (x=0, 0.05, 0.10, 0.15) (PZCT). X-ray diffraction (XRD) technique and scanning electron microscopy (SEM) were used to study the structural and microstructural properties of the compounds, respectively. The XRD study confirmed the formation of compounds at room temperature. Microstructural analysis of the surface of the compounds exhibits that there is a change in grain size, shape and density on introduction of cerium (Ce) in PZCT. Detailed studies of the dielectric properties reveal that PZCT show: (i) increase in T c on increasing Ce concentration and (ii) improvement in dielectric constant and ac conductivity.