Abstract The cure characteristics of thermosetting resins are affected by the presence of reinforcements as a result of surface–resin interactions. Surface treatments and sizing can significantly affect such interactions; hence, sizing or surface treatment selection may significantly affect resin cure characteristics. This is of particular concern in the processing of composite materials, since neat resin cure characteristics often will not provide the appropriate basis for predicting the cure behavior of the composite. In this work, the effect of several commercially sized S-2 glass systems on the cure of vinyl–ester resin was investigated. Generally, a significant increase in the cure rate of the glass-modified systems is observed. Furthermore, a relationship between the surface energy characteristics of the fibers and the degree of cure acceleration is established, and possible mechanisms for the effect are discussed. It is apparent that sizing selection can significantly affect cure processes for vinyl–ester systems.