AbstractPhotocatalytic syngas production is an attractive option to efficiently generate a feedstock for the Fischer‐Tropsch processes that can produce liquid fuels and other chemicals. One‐pot photocatalytic production of syngas (H2+CO) with specific and controllable ratios of H2/CO has proven to be a significant challenge to date. In this work, single Co2+ sites loaded onto carbon nitride (Co@C3N4) is combined with black phosphorus (BP) to form a hybrid material, which is capable of simultaneous photocatalytic evolution of H2 and CO. H2/CO syngas ratios can be controlled in the range from 0.30 to 5.16 by changing the % weight of BP in this system or by the addition of CoCl2 in the reaction solution. Maximum total gas evolution of 70 μmol g−1 h−1 was achieved with 20 wt % BP (BP20%/Co@C3N4) at a H2/CO ratio of 2.