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In this study, a system of photocatalysis for NAD+ regeneration of enzymatic catalysis was constructed. The optimal conditions for the coupling reaction of photocatalysis and biocatalysis were explored. Blue light was chosen for the efficient reaction and the optimal concentration of VB2 (vitamin B2, riboflavin) was determined. NAD+-dependent (R)-1-phenylethanol dehydrogenase was used in the reaction for transforming (R)-1-phenylethanol to acetophenone. The byproducts of the reaction were just H2O and O2 by means of catalase. The coupling reaction of catalysis and photocatalysis can be used for obtaining (S)-1-phenylethanol through racemization of 1-phenylethanol.