Calcium chloride methanol addition compounds are promising sorbent candidates, which can not only be used for thermal energy storage but also for providing evaporative cooling in industrial applications using low-grade heat. The methanolate dissociation occurs within the working temperature range of low temperature cooling systems. Methanol has a low freezing point and high operating pressure and is less toxic and corrosive than ammonia as refrigerant. In solid-gas reactions the overall specific cooling capacity mainly depends on the sorption rate of the reaction. In general the reaction pattern follows a complex mechanism, in which the formation of intermediate phases and structural changes might occur. In this study a comprehensive micro-scale analysis on the effect of the methanol partial pressure, the thermal history of the calcium chloride, the dissociation temperature and subsequent sorption-desorption cycling on the sorption rate has been carried out. Results show that thermodynamic conditions as well as the thermal history and physicochemical properties of the material have a great influence on the sorption rate, whereas only a marginal dependence between the regeneration temperature and the sorption process was observed.