Iron　vanadate　(FeVO4)　is　a　promising　photoanode　for　photoelectrochemical　(PEC)　water　splitting　because　of　its　unique　electronic　band　structure,　in　particular　the　bandgap　of　2.1　eV.　However,　its　PEC　performance　is　limited　by　the　charge　recombination　at　transparent　conducting　substrate/photoanode　interface.　Herein,　we　demonstrate　that　the　introduction　of　an　ultrathin　(1.1　nm)　TiO2　layer　between　FTO　and　an　FeVO4　photoanode　by　atomic　layer　deposition　(ALD)　technology　can　well　address　the　issue　of　interfacial　charge　recombination,　this　is　because　the　large　valence　band　offset　between　TiO2　and　FeVO4　can　effectively　suppress　back　hole　transfer　and　subsequently　improve　charge　separation.　As　expected,　the　modified　photoanode　exhibited　an　enhanced　PEC　water　splitting　performance.　We　believe　that　the　strategy　of　fabricating　an　ultrathin　TiO2　interfacial　layer　as　a　hole　blocking　barrier　can　also　benefit　other　photoanodes.　©　The　Royal　Society　of　Chemistry.