The conventional gravimetric method and positron lifetime spectroscopy have been used to investigate the effect of glass fiber orientation on the diffusion behavior of seawater in epoxy-based composite samples with glass fiber orientations of 0 and 458. The equilibrium mass uptake of seawater in 45 and 08 orientation composites has been found to be 2.77 and 1.57%, respectively. The diffusion process is non-Fickian in a 458 fiber oriented composite, whereas it is Fickian in a 08 oriented composite. Free-volume data for 458 fiber oriented composites indicates swelling upon the sorption of seawater leading to structural relaxation, and hence the diffusion becomes non-Fickian. On the other hand, a 08 fiber orientation sample exhibits no swelling, and this suggests that water diffusion to the fiber-resin interface through the resin matrix is impeded by the large number of bonds. A polymer-fiber interaction parameter determined from these results also further supports the idea that interface interaction in a 458 fiber oriented composite is less than that in a 08 fiber oriented composite. Positron and gravimetric results support this argument.