| Summary: | The epoxidation of grape seed oil in supercritical CO<sub>2</sub>, to the best of our knowledge, has been only superficially described in the literature, apart from a short communication and our own previous published work on the topic. In this work, a thorough study of the performance of the supercritical epoxidation of grape seed oil is performed in a wide range of conditions, and the kinetic parameters of the supercritical epoxidation of vegetable oils are reported for the first time in the literature. The experimental work has covered a 40–60 °C temperature range at 150 bar, sampling during a period of 48 h. The nature and extent of the side reactions and secondary products obtained have been evaluated, being hydrolysis products and their oligomerization derivatives the major by-products. Reaction rate constants (10<sup>−2</sup> h<sup>−1</sup> order) and activation energy parameters were finally calculated from the experimental conversion and epoxy yield data to establish the effect of temperature on the kinetics of the process.
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