Composite films were prepared by two different routes: lead zirconate titanate (PZT) particles coated with polyaniline (PAni) dispersed in a polymeric matrix of polyvinylidene fluoride (PVDF); and PZT particles and PAni powder dispersed separately in the polymer matrix. The electrical conductivity of the particles was controlled by the protonation and de-protonation of PAni in solution with controlled pH. The results indicate that the percolation threshold of the composite made of PZT coated with a conductive layer (PZT-PAni) is in the range of 20 vol.% to 30 vol.% of PZT-PAni. The PZT-PAni/PVDF composite redoped in solution with pH 3.7 showed the best results in terms of longitudinal piezoelectric coefficient (d 33 ) in samples containing 30 vol.% of ceramic particles due to the equilibrium between conduction and poling effects on the composite. The poling process of the composite sample required just 5 MV/m electric field applied during 15 min. Furthermore, the composite was used as sensor in structural health monitoring (SHM), showing the possibility to propose it as a functional material.