Curing kinetics of a vinylester-urethane hybrid (VEUH) resin consisting of vinylester resin (VE) diluted in styrene and novolac type polyisocyanate (NPI) have been studied by differential scanning calorimetry (DSC). As VEUH is crosslinked via free radical polymerisation between the vinyl functions of styrene and VE, and polyaddition reaction between the secondary -OH groups of VE and -NCO of NPI, it was necessary to study these reactions separately. This was achieved by studying the curing with and without incorporating the NPI. The curing reaction was monitored by measuring the heat of reaction under isothermal and dynamic temperature conditions. Models describing the curing were developed, which are in good agreement with the experiments. A comparison between the curing of the VEUH and the VE resin without NPI leads to the conclusion that the curing of the VEUH as accessed by DSC is dominated by the radical polymerisation of styrene with VE although the two reactions are not time separated.