Temperature-dependent vapor pressures of solid explosives and their byproducts are calculated to an accuracy of 0.32 log units using a modified form of the conductor-like screening model for real solvents (COSMO-RS). Accurate predictions for solids within COSMO-RS require correction for the free energy of fusion as well as other effects such as van der Waals interactions. Limited experimental data on explosives is available to determine these corrections, and thus we have extended the COSMO-RS model by introducing a quantitative structure-property relationship to estimate a lumped correction factor using only information from standard quantum chemistry calculations. This modification improves the COSMO-RS estimate of ambient vapor pressure by more than 1 order of magnitude for a range of nitrogen-rich explosives and their derivatives, bringing the theoretical predictions to within typical experimental error bars for vapor pressure measurements. The estimated temperature dependence of these vapor pressures also agrees well with available experimental data, which is particularly important for estimating environmental transport and gas evolution for buried explosives or environmentally contaminated locations. This technique is then used to predict vapor pressures for a number of explosives and degradation products for which experimental data is not readily available.