The cross-linking kinetics and the rheological behavior of a polyurethane system during curing are investigated by DSC and small amplitude oscillatory shear rheometry. In this study, isoconversional methods are applied to understand the reaction complexity. The activation energy depends on the extent of conversion. It can be shown that three parallel reactions occur during the evolution of the global reaction in non-isothermal conditions. An original multi-step model can involve these three parallel independent reactions. Dynamic viscosity is measured as a function of time and is found independent of shear rate. Isothermal viscosity rise is related to reaction extent by a phenomenological model. The gelation time is determined by the tandelta crossover at different frequencies.