Poly(vinyl) alcohol (PVA)/nanosilica (SiO2) based electrospun nanofibers has been deposited on wood substrate by means of the roll electrospinning process. The nanofibrous coating was hydrophobized by self-assembled monolayers of octadecyltrichlorosilane (OTS) via a solgel dipping process. The PVA/SiO2 nanofiber coating and OTS hydrophobized coating were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and energy dispersive X-ray analysis (EDXA). All methods confirmed the formation of OTS monolayers on hybrid coatings. The adhesive strength and resistance to scratch of nanofibers coating was also evaluated.