Vitamin A is very sensitive to chemical degradation caused by oxygen, light, heat, and other stress factors. If light and oxygen are excluded, the dominant degradation reaction for vitamin A derivatives is heat-induced formation of kitols, that is, dimers or higher oligomers. In this study vitamin A esters were used as model systems to evaluate microcalorimetry as a tool for monitoring the stability of heat sensitive substances. To obtain more knowledge about the model reaction, analytical investigations (supercritical fluid chromatography) were also performed. Because analytical and microcalorimetry data were consistent, a quantitative description of the kinetics and thermodynamics of the kitol formation reaction could be obtained. Aside from the academic motivation, this is important for practical purposes such as shelf life stability of vitamin A in feed, food, and pharmaceutical products. The vitamin A stability of a given sample can easily be predicted from the initial heat flow in a simple microcalorimetry experiment. Compared to conventional stability tests, this offers savings of money and time.