A spin-coating process integrated with an ozone-induced graft polymerization technique was applied in this study. The purpose was to improve the poor interfacial compatibility between a selective layer of poly(2-hydroxyethyl methacrylate) (PHEMA) and the surface of a poly(vinylidene fluoride) (PVDF) substrate. The composite membranes thus fabricated were tested for their pervaporation performance in dehydrating an ethyl acetate/water mixture. Furthermore, the composite membranes were characterized by field emission scanning electron microscopy (FE-SEM) for morphological change observation and by Fourier transform infrared spectroscopy equipped with attenuated total reflectance (ATR-FTIR) for surface chemical composition analysis. Effects of grafting density and spin-coating speed on pervaporation performance were examined. The composite membrane pervaporation performance was elucidated by means of free volume and depth profile data obtained with the use of a variable monoenergy slow positron beam (VMSPB). Results indicated that a smaller free volume was correlated with a higher pervaporation performance of a composite membrane consisting of a selective layer of spin-coated PHEMA on a PHEMA-grafted PVDF substrate (S-PHEMA/PHEMA-g-PVDF). The composite membrane depth profile illustrated that an S-PHEMA layer spin-coated at a higher revolutions per minute (rpm) was thinner and denser than that at a lower rpm.