Absolute measurements of the rate coefficient of the title reaction are reported from 251 to 373 K using the laser-induced fluorescence–pulsed-laser photolysis technique, together with room-temperature relative rate determinations using a simulation chamber. These are the first reported values of this rate coefficient, which demonstrates a predominantly negative temperature dependence that is more pronounced than with other epoxides, suggesting that pre-reactive complexes contribute to the overall reactivity, and that these complexes are comparatively stable for OH + cyclohexene oxide, which may result from its bicyclic structure. This work provides new insights into the lesser-studied reactivity of the epoxide functionality.