A simple setup that combines the grinding action of a ball mill with the analytical power of NMR spectroscopy has been developed, proving to be an excellent platform for the study of sublimation phenomena. Specifically, the fine sizing of the milling action ensures a high number of contacts between solid particles, which results in intensive interaction between the ground species, and a constant refresh of the surface available for sublimation. Simultaneously, the use of a benchtop NMR system to analyze the sublimate species allows for quantitative and qualitative evaluation of analytes, without overload problems and with the eventual advantage of a wide range of solvents and standards for quantification purposes in accordance with the observables. The level of precision in repeating the analyses proved reliable, as long as all parameters were continuously monitored of reproducibility of the experiments due to the high sensibility of the studied systems. Future setup improvements should focus on an automation of the gas flow regulation, the ability to regulate the milling jar and the gas temperatures, and on the filtration system.