The standard state enthalpy of formation and the enthalpy of sublimation are essential thermochemical parameters determining the performance and application prospects of energetic materials (EM). Direct experimental measurements of these properties are complicated by low volatility and high heat release in bomb calorimetry experiments. As a result, the uncertainties in the reported enthalpies of formation for a number of even well-known CHNO-containing compounds might amount up to tens kJ mol⁻¹, while for some novel high-nitrogen molecules they reach even hundreds of kJ mol⁻¹. The present study reports a facile approach to determining the solid-state formation enthalpies comprised of complementary high-level quantum chemical calculations of the gas-phase thermochemistry and advanced thermal analysis techniques yielding sublimation enthalpies. The thermogravimetric procedure for the measurement of sublimation enthalpy was modified by using low external pressures (down to 0.2 Pa). This allows for observing sublimation/vaporization instead of thermal decomposition of the compounds studied. Extensive benchmarking on nonenergetic and energetic compounds reveals the average and maximal absolute errors of the sublimation enthalpies of 3.3 and 11.0 kJ mol⁻¹, respectively. The comparison of the results with those obtained from the widely used Trouton–Williams empirical equation shows that the latter underestimates the sublimation enthalpy up to 140 kJ mol⁻¹. Therefore, we performed a reparametrization of the latter equation with simple chemical descriptors that reduces the mean error down to 30 kJ mol⁻¹. Highly accurate multi-level procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach were used to calculate theoretically the gas-phase formation enthalpies. In several cases, the DLPNO-CCSD(T) enthalpies of isodesmic reactions were also employed to obtain the gas-phase thermochemistry for medium-sized important EMs. Combining the obtained thermochemical properties, we determined the solid-state enthalpies of formation for nearly 60 species containing various important explosophoric groups, from common nitroaromatics, nitroethers, and nitramines to novel nitrogen-rich heterocyclic species (e.g., the derivatives of pyrazole, tetrazole, furoxan, etc.). The large-scale benchmarking against the available experimental solid-state enthalpies of formation yielded the maximal inaccuracy of the proposed method of 25 kJ mol⁻¹.