Developing robust, multifunctional photocatalysts that can facilitate both hydrogen evolution via photoreforming of water and gas phase CO2 photoreduction is highly desirable with the long-term vision of integrated photocatalytic setups. Here, we present a step-change in the family of boron oxynitride materials by introducing the first example of a B-doped boron oxynitride (B-BNO). This material resolves an on-going bottleneck associated with BN-based materials, i.e. the lack of photoactivity under visible light. Detailed EPR studies revealed distinct hyperfine interactions between the free oxygen radicals and 3 neighbouring boron nuclei. This confirmed isolated OB3 sites, which contribute to band gap narrowing, as the radical species and origin of paramagnetism in BNO materials. We show that B-BNO can facilitate both liquid phase H2 evolution and gas phase CO2 photoreduction, using UV-Vis and deep visible irradiation (λ > 550 nm), without any co-catalysts. The evolution rates, quantum efficiencies, and selectivities observed for both reactions with B-BNO exceed those of its porous BNO counterpart, P25 TiO2 and bulk g-C3N4.