A series of simultaneous interpenetrating polymer networks (SINs) composed of polyurethane (PU) and vinyl ester resin (VER) was prepared from different rigid phase components, where the pendent hydroxyl groups of VER were retained or capped, and through different molding processes, i.e., hand-casting dr reaction injection molding (RTM). It was recognized that the occurrence of chemical binding between PU and VER networks through the reaction of the diisocyanate and the pendent hydroxyl groups of VER played an important role in determining the mechanical properties of these SINs. The hand-cast SINs, with VER containing pendent hydroxyl groups as the rigid phase component and with these pendent hydroxyl groups counted for the metering of diisocyanate besides that due to polyether polyol and chain extender of PU phase, behaved like the hybrid polyester matrix. For the RIM-molded SIN samples, an obvious reinforcing effect of VER network, whose pendent hydroxyl groups were capped with acetyl groups, upon PU network was observed. These results correlated well with the knowledge of polymerization kinetics and morphology development of these PU/VER SINs.