The DFF-B3LYP method, with basis set 6-31G*, is employed to optimize molecular geometries and electronic structures of eighteen nitramines. The averaged molar volume (V) and theoretical density (rho) are estimated using the Monte-Carlo method based on 0.001 electrons/bohr(3) density space. Subsequently, the detonation velocity (D) and pressure (P) of the explosives are estimated by using the Kamlet-Jacobs equation on the basis of the theoretical density and heat of formation (Delta H-f), which is calculated using the PM3 method. ne reliability of this theoretical method and results are tested by comparing the theoretical values of rho and D with the experimental or referenced values. The theoretical values of D and P are compared with the experimental values of electric spark sensitivity (E-ES). It is found that for the compounds with metylenenitramine units (-CH2N(NO2)-) in their molecules (such as ORDX, AcAn and HMX) or with the better symmetrical cyclic nitramines but excluding metylenenitramine units (such as DNDC and TNAD), there is a excellent linear relationship between the square of detonation velocity (D-2) or the logarithm of detonation pressure (lg P) and electric spark sensitivity (E-ES). This suggests that in the molecular design of energetic materials, such a theoretical approach can be used to predict their E-ES values, which have been proven to be difficult to predict quantitatively or to synthesize.