Structured lead zirconium titanate (PZT)–epoxy composites are prepared by dielectrophoresis. The piezoelectric and dielectric properties of the composites as a function of PZT volume fraction are investigated and compared with the corresponding unstructured composites. The effect of poling voltage on piezoelectric properties of the composites is studied for various volume fractions of PZT composites. The experimentally observed piezoelectric and dielectric properties have been compared with theoretical models. Dielectrophoretically structured composites exhibit higher piezoelectric voltage coefficients compared to 0–3 composites. Structured composites with 0.1 volume fraction of PZT have the highest piezoelectric voltage coefficient. The flexural strength and bending modulus of the structured and random composites were analyzed using three-point bending tests.