With emerging applications of the internet of things, technologies based on flexible materials draw much attention. In this aspect, flexible multiferroic materials might play a vital role in technologies such as energy harvesting, memory, sensor and much more. This work reports the pyroelectric studies on multiferroic polymer composite films coated on flexible substrates for pyroelectric energy conversion. Polyvinylidene fluoride/cobalt ferrite composite films were prepared by spin coating technique with different weight percentages of cobalt ferrite. The ferroelectric β-phase of polyvinylidene fluoride in composite films were confirmed by Fourier transform infrared spectroscopy. The polar β-phase of PVDF nucleated by the incorporation of CoFe2O4, through CF2 interaction with CoFe2O4 particles, in PVDF/CoFe2O4 composite films. The composite films reveal an increase in dielectric constant with the addition of cobalt ferrite. A maximum figure of merit value of 20.21% was observed in 15 wt % of CoFe2O4 composite film by using phase sensitive approach. The maximum magnetization was observed in 20 wt % of CoFe2O4 composite film. Improved film quality improves the pyroelectric coefficient and figure of merit for pyroelectric energy conversion.