A high performance of catalyst material for delaying polyurethane (PU) polymerization at room temperature and rapid PU polymerization at preferred temperature still remains a great challenge because of adverse activation. Herein, N-heterocyclic carbene (NHC)-FeCl3 complex catalyst is developed and optimized to control the PU polymerization. The effects of PU polymerization degree and reaction kinetic is remarkably altered by the NHC-FeCl3 catalyst. It is found that the as-synthesized NHC-FeCl3 shows efficient catalytic activity as very low viscosity changes in room temperature and fast curing (3 h) at 60 °C, which proves considerable catalytic activity than the commercial catalyst and none-catalyst system. Based on DSC measurement, an increase in reaction rate is observed to PU polymerization with NHC-FeCl3. The PU polymerization reaction has excellently initiated at 60 °C by NHC-FeCl3 catalyst, where NHC act as Lewis acid and interacts with polyol, and FeCl3 reacts with isocyanate by electrophilic reaction.