The relationship between the electrostatic sensitivity and the molecular structure for 16 kinds of nitramine compounds and 34 kinds of nitro aromatic compounds were established based on the theory of the electrotopological state (E-state). Quantitative structure-property relationship(QSPR) model by Multiple linear regression method were established. The correlation coefficient and standard deviation of the nitramine compounds were 0.782 and 0.217, respectively, and those of the nitro aromatic compounds were 0.717 and 0.195. Analysis of the model show that there is a better correlation between the electrotopological state indices for atom type and the electrostatic sensitivity of the nitro class energetic materials, and it can be used to predict the electrostatic sensitivity of nitro compounds effectively. The electrical condition of atoms affects the electrostatic sensitivity importantly.