The massive growth of the electronics industry has increased the need for new active materials for various applications in electronic devices. Organic ferroelectrics such as Poly (vinylidene fluoride) or PVDF are highly preferred due to its less cost, easy fabrication, less weight and high Curie temperatures (Tc) compared to conventional inorganic ferroelectric materials. The ferroelectric nature and stability of PVDF can be altered by choosing appropriate substrates to fabricate thin films. In our work, we examine graphene as a support substrate for crystallization of PVDF. We expect that graphene lattice has a strong epitaxial interaction with PVDF chains with specific symmetry providing excellent ferroelectric nature with stability because of a lattice match between graphene and PVDF. Hence, piezoresponse force microscopy is used as a novel probe microscopy tool to characterize the ferroelectric properties by polarization writing and reading on the surface of the heterostructures.