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Understanding species distribution across habitats and environmental variables is important to inform area-based management. However, observational data are often lacking, particularly from developing countries, hindering effective conservation design. One such data-poor area is the Gulf of Guinea, an understudied and biodiverse region where coastal waters play a critical role in coastal livelihoods. Here, we describe the results of the largest national-scale Baited Remote Underwater Video Systems (BRUVS) survey in the region, aiming to understand the effects of several environmental variables on fish community composition and diversity. From 2018 to 2020, we successfully deployed 417 benthic BRUVS in the coastal waters of the São Tomé and Príncipe (STP) archipelago. Species richness and relative abundance were higher in deeper waters, on steeper slopes, and in rocky reef habitats. Nevertheless, maerl and sand habitats also hosted unique, and economically important species. Our results potentially indicate historical impacts of fishing in the archipelago, especially in São Tomé Island, where observed fishing effort is higher. Indeed, abundance of large predatory fish was low in both islands and abundance of species targeted by artisanal fisheries was lower in São Tomé than in Príncipe. Our results provide crucial information supporting the designation and future monitoring of marine protected areas in STP. [ABSTRACT FROM AUTHOR]