Pb1-xCax[(C0.5W0.5)(0.05)Ti-0.95]O-3 ceramics with x = 0.24, 0.30 and 0.35, are prepared by a solid state reaction of oxides. Deviations from nominal chemical compositions and formation of segregated phases different from modified lead titanate perovskites, are studied. Pyro- and non-pyroelectric currents excited in the material by a thermal wave are investigated and related to mobility of electrical charges in the materials.