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The authors investigate the effect of electrode material and charge injection on the breakdown electric field of poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer. The results indicate that the breakdown is mainly initiated at electrode-polymer interfaces, the properties of which are controlled by metal materials and deposition conditions. Interfaces with lower leakage currents display higher breakdown fields. Terpolymer films with Al and Cr electrodes have lower leakage current and higher breakdown field compared to those with Au and Ag electrodes. The difference in charge injection and breakdown field is attributed to both the existence of interfacial blocking layers and the difference in Schottky barrier height.