PZT/LCT/PA (lead zirconate titanate Pb(Zr1−xTix)O3/Liquid crystalline thermosets/polyamide) composites of 0-3 connectivity were fabricated by hot-pressing. Commercially available PZT powder was calcined at different temperatures for the optimization of the composite properties. The phase transition during calcination of the powder was studied by x-ray diffraction and the particle size by light scattering and scanning electron microscopy. The relative permittivity εr, piezoelectric charge constant d33, conductivity σ and elastic modulus E of the composites were found to increase with increasing ceramic volume fraction φ. The obtained d33 and g33 values of this newly developed PZT/LCT/PA composite with 50 vol% PZT using a low poling voltage of 60 kV cm−1 and poling time of 30 min are 42 pC N−1 and 65 mV m N−1, respectively, which are high values for this volume fraction in comparison with the other 0-3 composites reported. Good agreement was found between the experimental data of relative permittivity and piezoelectric constants with several theoretical models (Jayasundere, Yamada and Lichtenecker) of 0-3 composites. In order to assess the correlation of the experimental data with the theoretical models, the experimental data obtained from PZT/PA composites were also included.