Understanding the mechanism of shock-induced chemical reaction in secondary explosives is necessary to pursue the development and the safe use of new explosives having high performance and low sensitivity. In an effort to understand the mechanism, the energy transfer rates of such secondary explosives as PETN(I), PETN(II), delta-HMX, alpha-HMX, beta-HMX, RDX, ANTA, DMN, and NM have been evaluated based on the formula derived by Fried and Ruggiero [Fried, L. E.; Ruggiero, A. J. J. Phys. Chem. 1994, 98, 9786]. The energy transfer rates were determined in terms of the density of vibrational states and the unharmonic vibron-phonon coupling term, which were calculated by using a flexible potential containing both intra- and intermolecular terms. For the secondary explosives, a good correlation was found between the energy transfer rates and the impact sensitivity. The energy transfer rates are several times faster for the explosives with higher sensitivity such as PETN, HMX, and RDX than those with lower sensitivity such as ANTA, DMN, and NM. The calculations presented suggest the energy transfer rate in secondary explosive crystals is a significant factor in their sensitivity and introduction of double bond, or hydrogen bonds, or caged structure into secondary explosives is expected to decrease the sensitivity.