Metal　nanocrystals　(NCs)　have　been　recognized　as　an　important　class　of　nanomaterials　by　virtue　of　their　unique　surface　plasmon　resonance　(SPR)　effect　and　pivotal　roles　as　electron　traps　in　photocatalysis.　Nevertheless,　it　is　still　challenging　to　unambiguously　unravel　and　simultaneously　harness　the　dual　synergistic　roles　of　metal　NCs　in　a　single　photocatalytic　system　for　solar-to-chemical　energy　conversion.　Herein,　an　efficient　ligand-triggered　electrostatic　self-assembly　strategy　was　developed　to　achieve　the　spontaneous　and　monodispersed　attachment　of　Au　NCs　onto　1D　WO3　nanorods　(NRs)　via　pronounced　electrostatic　attractive　interaction,　in　which　tailor-made　positively　charged　Au　NCs　were　closely　integrated　with　negatively　charged　WO3　NRs.　The　intimate　integration　of　Au　NCs　with　WO3　NRs　at　the　nanoscale　could　significantly　benefit　the　extraction,　separation,　and　migration　of　plasmon-induced　energetic　hot　carriers　over　Au　NCs　and　promote　the　separation　of　photogenerated　charge　carriers　over　the　WO3　substrate.　Such　a　cooperative　synergy　stemming　from　SPR　and　the　electron-withdrawal　effects　of　the　Au　NCs　resulted　in　distinctly　enhanced　photoredox　catalytic　performances　for　plasmonic　photocatalysis　under　both　simulated　solar　and　visible　light　irradiation.　Our　study　highlights　the　significance　of　utilizing　a　rational　interface　design　between　metal　NCs　and　semiconductors　for　excavating　the　multifarious　roles　of　metal　NCs　in　substantial　solar　energy　conversion.