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Most of previous photocatalysts contain metal species, thus exploring a metal-free photocatalyst is still challenging. A metal-free photocatalyst has an advantage for the development of economical and non-toxic artificial photosynthesis system and/or environmental purification applications. In this study, rhombohedral boron monosulfide (r-BS) was synthesized by a high-pressure solid-state reaction, and its photocatalytic properties were investigated. r-BS absorbed visible light, and its photocurrent action spectrum also exhibited visible light responsivity. The r-BS evolved hydrogen (H2) from water under ultraviolet (UV) as well as under visible light irradiation, and its internal quantum efficiency reached 1.8% under UV light irradiation. In addition to the H2 evolution reaction, the r-BS photocatalyst drove carbon dioxide (CO2) reduction and dye oxidation reactions under UV irradiation. Although bare r-BS was not so stable under strong light irradiation in water, cocatalyst modification improved its stability. These results indicate that r-BS is a new class of non-metal photocatalyst applicable for H2 production, CO2 reduction, and environmental purification reactions. [ABSTRACT FROM AUTHOR]