The emission of volatile organic compounds (VOCs) significantly contributes to the atmospheric oxidative balance and secondary organic aerosol (SOA) formation, thereby influencing global climate. Reactive substances such as methane, non-methane hydrocarbons, dimethyl sulfide, and halocarbons in the ocean are important components of VOCs, primarily produced through biological and non-biological processes. To date, substantial research has been conducted on the source-sink processes of marine VOCs and their response mechanisms to environmental factors. However, much of this research has focused on biological processes, overlooking the contributions of photochemical processes involving dissolved organic matter (DOM) in the sea surface (micro) layer, which may result in an underestimation of their emissions. In recent years, marine photochemistry, particularly the photochemical processes of DOM in the sea surface micro-layer, has gained increasing attention. This review systematically examines the research progress on the sources and emission fluxes of marine VOCs, with a focus on the mechanisms of VOCs production via DOM photochemistry, their response to environmental factors, and their implications for climate change. Furthermore, future research directions are proposed from the perspectives of technological innovation, mechanism exploration, and environmental assessment. Long-term observation and simulation studies of photochemical processes of DOM in the sea surface micro-layer are highlighted as crucial for revealing the response of marine VOCs photochemical production to human activities and its impact on climate change.