In this study, dehydrofluorinated poly(vinylidene fluoride)/lead zirconate titanate composites (DHF-PVDF/PZT) were prepared via solution casting, followed by hot pressing. The synergistic effect of dehydrofluorination and PZT addition on the polar phase content and electrical properties of DHF-PVDF/PZT was investigated. The polar phase content of DHF-PVDF increases to 60.76% with the introduction of 9.42% carbon−carbon double bonds and then to 84.96% with the addition of PZT. The dielectric and ferroelectric properties of DHF-PVDF/PZT composites are enhanced under the synergistic effect of PZT addition and dehydrofluorination. The dielectric constant of DHF-PVDF/8 wt %PZT at 1 kHz significantly increases (∼16.0) compared to DHF-PVDF (∼11.9), while dielectric loss remains low. DHF-PVDF/8 wt % PZT also exhibits a high discharge energy density (∼6.43 J/cm 3 at 2500 kV/ cm) and efficiency (∼45.6%), attributed to the strong localized electric field generated in the composites. The study leads toward a way of developing PVDF/PZT composites for high-energy density capacitors.