The ring opening between BCC with di-amine by conventional heating (130 °C for 48 h) is a time-consuming and non-efficient process. This work has been aiming at accelerating its ring-opening reaction by a microwave radiation process. Besides, catalyst and solvent selections of this PU reaction system, the microwave power output, radiation time, catalyst and reaction media were major consideration of this research. A catalyst, TBAC or LiBr had been applied on each microwave-assisted ring-opening polymerization of BCC with Jeffamine D-2000. A similar average molecular weight of NH2-PU oligomer was obtained from a 50 min microwave radiation by using 50 W power output. The radiation system with TBAC as catalyst, and it resulted in a formation of NH2-PU oligomer with Mn and Mw were 12,997 and 15,580, and that of 10,882 and 13,508 with LiBr as catalyst. The solvent polarity, catalyst solubility and microwave output energy in this radiation system were considered as important factors for this new green process.