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An active and stable photocatalyst to directly split water is desirable for solar-energy conversion. However, it is difficult to accomplish overall water splitting without sacrificial electron donors. Herein, we demonstrate a strategy via constructing a single site to simultaneously promote charge separation and catalytic activity for robust overall water splitting. A single Co1-P4 site confined on g-C3N4 nanosheets was prepared by a facile phosphidation method, and identified by electron microscopy and X-ray absorption spectroscopy. This coordinatively unsaturated Co site can effectively suppress charge recombination and prolong carrier lifetime by about 20 times relative to pristine g-C3N4, and boost water molecular adsorption and activation for oxygen evolution. This single-site photocatalyst exhibits steady and high water splitting activity with H2 evolution rate up to 410.3 μmol h−1 g−1, and quantum efficiency as high as 2.2 % at 500 nm. [ABSTRACT FROM AUTHOR]