Composite films were prepared using poly(vinyl alcohol) (PVA) and graphene oxide (GO) by solution casting technique, and their morphology, physical, and mechanical properties were studied. The hexagonal array of diffraction peaks reveals that GO is uniformly distributed in the polymer matrix, indicating the excellent compatibility of the filler with the polymer. GO incorporation does not change PVA degree of crystallinity, but increases the thermal stability (the temperature of degradation) of the polymer. For PVA/GO composite film with 4 wt% of the filler, the tensile strength as well as the Young’s modulus increases compared to that of the neat PVA film. At the same time, the GO addition led to a sharp decrease in the elongation at break of the sample. In order to improve the plasticity of the composite film, cold rolling processing of the composite PVA/GO film was performed which is known to suppress the tendency of nanocomposite to brittle fracture.