The successful merging of photochemical and electrochemical strategies has recently opened new avenues in synthesis endeavours, offering unique possibilities for the generation and manipulation of radical intermediates. This chapter offers an overview about recent contributions in the field, classifying the available examples according to the operating mechanism, which may involve either a homogeneous photocatalytic cycle or a different photoinduced event. In terms of synthetic applications, the merger of photochemistry and electrochemistry enables to realize a plethora of arylation processes of both aromatic and aliphatic fragments, oxidations, as well as the forging of C–heteroatom bonds.