The development of energetic binders with suitable energetic plasticizers is required to enhance the mechanical properties and to reduce the glass transition temperature of propellant and explosive formulations. The compatibility of the energetic binder poly(3-nitratomethyl-3-methyloxetane) (polyNIMMO) with five different energetic plasticizers viz. bis(2,2-dinitro propyl) acetal (BDNPA), dinitro-diaza-alkanes (DNDA-57), 1,2,4-butanetriol trinitrate (BTTN), N-N-butyl-N'(2-nitroxy-ethyl) nitramine (BuNENA) and diethyleneglycoldinitrate (DEGDN) was studied by differential scanning calorimetry (DSC), rheology, and DFT methods. The results obtained for the pure binder were compared with the results obtained for the binder/plasticizer blend in regard of the decomposition temperature and the format of the peak indicated the compatibility of poly-NIMMO with the plasticizers. The glass transition temperatures of the blends were determined by low temperature DSC and showed desirable lowering of glass transition temperature with single peak. The rheological evaluation revealed that the viscosity of the binder is considerably lowered by means of flow behavior upon addition of 20% (w/w) plasticizer. The addition of BuNENA and DEGDN has maximum effect on the lowering of viscosity of polyNIMMO. The predicted relative trend of interaction energies between plasticizer and binder is well correlated with the corresponding trend of viscosity of binder/plasticizer blends. These experimental studies verified by theoretical methods are valuable to design practical blends of new plasticizers and binders.