Cohesive energy density and solubility parameter of nitrate ester plasticizers，azide prepolymer and azide thermoplastic elastomers which consisted of different soft segment and hard segment were calculated respectively by molecular dynamics simulation method. The results show that the miscibility of azide prepolymer or azide thermoplastic elastomer with diethyl-eneglycol dinitrate (DEGDN), triethyleneglycol dinitrate (TEGDN) is better than that with (nitroglycerin) NG, (1,2,4-butanetrioltrinitrate) BTTN or NG+DEGDN; and PAMCMO shows much better miscibility with nitrate ester plasticizer than GAP, BAMO, AMMO. Although the solubility parameter of azide thermoplastic elastomers calculated is higher than that of prepolymer, the miscibility is still not well. The homopolymer of azide prepolymer show better miscibility with nitrate ester plasticizers than their copolymer with THF.