The　use　of　polymeric　carbon　nitride　(PCN)　for　photoredox　catalysis　is　innovating　and　promoting　toward　sustainable　energy　economy.　One　of　the　drawbacks　of　this　metal-free　photocatalyst　is　its　insufficient　charge　separation　and　transfer.　Herein,　a　metal-free　system　was　achieved　by　anchoring　PCN　on　conductive　carbon　cloth　(CCC).　CCC　in　this　system　facilitated　the　charge　separation　and　transport　of　the　photoexcitation　charges　when　PCN　films　were　illuminated.　Both　photoelectrochemical　water　oxidation　and　photocatalytic　overall　water　splitting　were　achieved,　and　the　performances　were　improved　two-fold　with　respect　to　the　powder　PCN.　©　2021　Wiley-VCH　GmbH