A basic set of 10 thermoset polymer–polymer interfaces has been identified to play a vital role in the technical and economic aspects of composite manufacturing (RIM/RTM, compression molding, autoclave lamination), recycling, repair, welding, and joining of polymer composites. Knowledge of the chemical interactions and molecular connectivity at these interfaces and their influence on processability and mechanical properties of the polymers and polymer composite is essential, and has been the focus of this research. Presented in this report are the results of an exploratory study performed to understand the interactions at the polymer–polymer interface and their influence on the interfacial fracture toughness of a thermoset vinyl ester, which is widely used in liquid molding applications. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 775–785, 1999