By moving from the concept of in situ analyses, we herein present an NMR in operando monitoring system of mechanochemically accelerated sublimations under a constant flow of a carrier gas. The developed setup permits the analysis of the sublimation rate of both single substances or mixtures by combining controlled variations of milling parameters, gas flow, and gas pressure with the analytical power of NMR spectroscopy. When applied to the study of selfdisproportionations of enantiomers by sublimation, such system confirmed previous assumptions through a new point of view and opened ways for studying unexplored aspects of the phenomenon. Taking one step further, the solid-solid interaction promoted by mechanochemistry has been applied to control the sublimation properties of an enantiopure species and the concept has been validated by cross experiments.