A study of the microstructure developing at the surface of glass fibers in a poly(vinyl acetate) (PVAc)/polyester blend is presented. Three different experimental methods are used: a technique based on the Wilhelmy method to measure the wettability of the fibers before curing, and both optical microscopy and atomic force microscopy in the pulsed-force mode to characterize potential phases splitting at the fiber–matrix interface after curing. It was found that, depending on the curing conditions and the concentration in PVAc, the surface treatment of the fiber could have a significant influence on the microstructure. For a concentration in PVAc lower than 5 wt% and a curing temperature of 80°C, extreme cases, such as the development of layers of one of the phases at the surface or the formation of lenses of one phase, were observed. In other cases, in particular for elevated temperatures and higher concentrations in PVAc, the fibers did not exert a significant influence on the morphology. It was also found that in such a reactive system, surface tension considerations alone are insufficient to explain the configuration of the phases at the surface of the fibers.