To investigate the structure of azidodeoxycellulose(AC) and the miscibility of AC with plasticzers,structure and solubility parameters were simulated by molecular mechanics (MM) method and molecular dynamics (MD) method with COMPASS force filed. Results show that the excellent agreement is obtained between the simulated and experimental data for vibrational frequencies and X-ray diffraction (XRD) spectra; the simulation value of solubility parameter for AC is 20.86 (J·cm^-3)^1/2 at 298 K. The predicted order of miscibility of AC with plasticizers is: triethylence glycol dinitrate(TEGDN)＞diethylence glycol dinitrate(DEGDN) ≈acetone＞nitroglycerin(NG) ＞1,2,4-butanetriol trinitrate(BTTN).