Two different mixed connectivity composites, consisting of a ferroelectric ceramic powder of calcium modified lead titanate (PTCa) dispersed in a polymer matrix, have been fabricated and their ferroelectric properties have been investigated. Hysteresis measurements have been conducted on composites of PTCa with a polar polymer of polyvinylidene trifluoroethylene (P(VDF-TrFE)) and PTCa with a thermosetting epoxy resin to determine the coercive fields and remanent polarization of the two different composites. The composites show noticeable differences in their behavior during poling along with the values of their piezoelectric coefficients, with the composite of PTCa/P(VDF-TrFE) showing enhanced piezoelectric activity over that of PTCa/epoxy. This paper reports on the polarization properties and the microstructural nature of the composites.