ABSTRACTThe present research work focused on the dielectric and electrical properties of silver (Ag) doped Pb(Zr,Ti)O3 (PZT) particles embedded in a matrix of poly(vinyl alcohol) (PVA) via solution casting technique. The structural analysis confirmed the presence of Ag particles and the microstructural study revealed that both Ag and PZT particles were successfully homogenized over the polymer matrix. The Ag–PZT–PVA composites showed enhanced dielectric properties over a wide range of frequency and the dielectric constant value of such composites was significantly increased to 366 (100 Hz) at 1.1 wt % filler loading. The percolation threshold of the Ag–PZT–PVA composites was found to be 0.9 wt %. The experimental result well fitted to the percolation theory. The enhancement of dielectric constant of the resulting composite systems might be attributed to the increment of conductivity of the interlayer between PZT and PVA due to the presence of Ag particles, which improved the space charge polarization and Maxwell–Wagner–Sillars (MWS) polarization effects. Furthermore, the remnant polarization of the unpoled Ag–PZT–PVA composites (2Pr ∼1.48 µC/cm2 for 1.1.wt % of Ag–PZT) has also improved, which is favorable for enhanced ferroelectric properties of the composites. The present findings of the composites might be exploited in the potential application of high performance energy storage devices. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45583.