Light-driven biocatalysis has emerged as a powerful approach to unlock new enzymatic reactivity modes. In this field, flavoenzymes are particularly effective, owing to the presence of a redox-active cofactor that can act as a photocatalyst. The irradiation with visible light therefore enables new catalytic functions, which complement the natural reactivity repertoire of flavoenzymes. Herein, we provide a comprehensive review of native and promiscuous photoenzymatic activities of flavin-dependent proteins. In addition, flavoenzyme-based synergistic systems with an exogenous photoredox catalyst are discussed.