Photocatalytic syngas production is an attractive option to efficiently generate a feedstock for the Fischer-Tropsch processes that can produce liquid fuels and other chemicals. Onepot photocatalytic production of syngas (H 2 + CO) with specific and controllable ratios of H 2 /CO has proven to be a significant challenge to date. In this work, single Co 2 + sites loaded onto carbon nitride (Co@C 3 N 4 ) is combined with black phosphorus (BP) to form a hybrid material, which is capable of simultaneous photocatalytic evolution of H 2 and CO. H 2 /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 CoCl 2 in the reaction solution. Maximum total gas evolution of 70 μmol g À 1 h À 1 was achieved with 20 wt % BP (BP 20% /Co@C 3 N 4 ) at a H 2 /CO ratio of 2.