This article described the preparation of copper calcium titanate (CCTO)-modified poly(vinylidene fluoride) (PVDF) by solution casting, and its dielectric properties, breakdown strength and tensile properties. The phase structure, crystal type and surface morphology of the membrane were determined using the methods of Fourier-transform infrared spectroscopy, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. The results showed that the comprehensive performance of the CCTO/PVDF membrane treated with a coupling agent with a quality ratio of 2% was better than that of the membrane without coupling agent treatment. When the content of CCTO was increased to 20%, the surface structure of the membrane was compacted, and the membrane’s breakdown strength and dielectric properties were high.