In this paper, the Maxwell–Wagner effect and the charge characteristics of the heterogeneous interface at the action of higher electric field and elevated temperature are investigated by means of electret technology. A composite membrane with a double-layer structure of a polypropylene (PP) film and a fluorinated ethylene propylene copolymer (FEP) film was made. After being polarized under electric field and elevated temperature, the component PP and FEP films of the composite membranes were separated. The charge density of the PP and FEP films was measured to analyze the characteristics of interfacial charge in the composite membrane. Experimental results directly prove that the charge characteristics at the interface of the composite membranes are consistent with the result calculated by the Maxwell–Wagner effect. The polarity of the interfacial charge can be switched by changing the polarity of the polarizing voltage. The characteristics of the accumulated interfacial charge are strongly dependent on the conductivity, which is affected by the temperature and the polarizing electric field. A new phenomenon, that is, the measured charge density is much higher than that calculated by the Maxwell–Wagner effect, is found. The reason is ascribed to the electret effect from the FEP and PP films. This research provides a new insight into the charge characteristics at the heterogeneous interface.