Photocatalytic　hydrogen　production　from　formic　acid　(FA)　is　a　daunting　challenge,　yet　an　essential　task　for　the　development　of　hydrogen　energy.　In　this　study,　a　p-NiO/n-TiO2　heterojunction　incorporating　7-nm　metallic　Ni　was　fabricated,　which　demonstrated　a　remarkable　localized　surface　plasmon　resonance　(LSPR)　effect.　Notably,　5　wt%　Ni/TiO2　exhibited　1271-fold　higher　photocatalytic　activity　(2416　μmol⋅g−1⋅h−1)　than　TiO2　alone　under　light　radiation　at　room　temperature.　The　experimental　investigations　revealed　the　excitation　of　distinct　components　via　irradiation　by　different　light　sources.　Visible　light-driven　hydrogen　production　was　predominantly　influenced　by　the　LSPR-induced　hot　electrons　and　holes　effects　of　Ni.　Further,　FA　molecules　simultaneously　lost　and　accepted　electrons　at　the　Ni0–Ti3+　and　Ni0–O2−　sites,　respectively,　generating　a　bidirectional　electron　transfer　behavior　with　“valley-shaped”　gas-sensitive　responses,　which　was　crucial　to　boost　the　activity.　Moreover,　the　photocatalytic　activity　was　mainly　attributed　to　the　heterojunction　and　defects　structure　under　UV　light　irradiation,　and　Ti3+,　VOs,　and　O2−　as　adsorption　sites　for　FA.　Thus,　the　synergistic　interplay　among　different　light　sources　could　effectively　boost　the　photocatalytic　hydrogen　production　performance.　Significantly,　this　research　reveals　that　the　LSPR　effect　of　metallic　Ni　can　effectively　regulate　electron　transfer　behavior　and　enhance　visible　light-driven　photocatalytic　activity.　©　2024　Elsevier　B.V.