This review delves into the innovative field of interfacial photoelectrochemical (iPEC) and photoelectrochemical (PEC) catalysis, the dynamic synthesis methodologies that seamlessly integrates electrochemical and photoredox catalysis for efficient and environmentally friendly reactions. Utilizing minute quantities of photocatalysts, visible light becomes a powerful tool, generating transient excited states to catalyze a spectrum of reactions through single-electron oxidation or reduction events. The review categorizes recent advancements, highlighting applications in organic synthesis, late-stage modifications, and the distinctive features of photoelectrochemical methodology. Despite being in its early stages, this synergistic approach holds great promise for propelling organic synthesis forward, with potential applications in large-scale synthesis and diverse late-stage functionalizations, including asymmetric catalysis and bioconjugation strategies for biomolecule modifications. This review explores the innovative realm of interfacial photoelectrochemical (iPEC) and photoelectrochemical (PEC) catalysis, seamlessly integrating electrochemical and photoredox processes for efficient reactions. Utilizing minimal photocatalysts, visible light catalyzes a range of reactions through single-electron events. Despite its early stage, this synergistic approach holds promise for advancing organic synthesis, with potential applications in late-stage modifications, and bioconjugation strategies for biomolecule modifications. image