We report that an NMR spectrometer equipped with a high-power LED light source can be used to study a fast enantioselective photocatalytic [2+2] cycloaddition. While traditional ex situ applications of NMR provide considerable information on reaction mechanisms, they are often ineffective for observing fast reactions. Recently, motivated by renewed interest in organic photochemistry, several approaches have been reported for in situ monitoring of photochemical reactions. These previously disclosed methods, however, have rarely been applied to rapid (<5 min) photochemical reactions. Furthermore, these approaches have not previously been used to interrogate the mechanisms of photocatalytic energy-transfer reactions. In the present work, we describe our experimental setup and demonstrate its utility by determining a phenomenological rate law for a model photocatalytic energy-transfer cycloaddition reaction.