Surface properties are extremely important for materials applied in the biomedical areas such as poly(vinyl alcohol)-PVA. The precise control of the surface characteristics on these materials may adjust and expand its applications. Here, we present a new strategy to tune the surface properties of poly(vinyl alcohol)/graphene oxide (PVA/GO) films by manipulation of GO particles (amount and level of oxidation) and also by in situ reduction of GO. Adopting a different approach from the methods currently proposed, the reduction process of GO was carried out by exposing the PVA/GO films to hydrazine vapor to maintain the degree of particle dispersion. Raman spectroscopy, contact angle (surface energy), X-ray diffraction, and atomic force microscopy were used to evaluate the interaction between PVA and GO particles and also to characterize graphene polymer composites properties at the surface of the films. The results indicated that there is a strong interaction between the GO particles and polar PVA groups mainly at a very specific stoichiometric ratio. Consequently, the surface properties of the PVA/GO films may be tuned by altering the concentration of the particles, their level of oxidation as well as by the exposure to hydrazine vapor. The impact of these affirmations is extremely important for improving the suitability of PVA in applications such as biomaterial, membranes, packaging, and others that need a rigorous control of surface properties. POLYM. COMPOS., 00:000-000, 2017.