Background:　In　the　context　of　modern　agriculture,　the　proliferation　of　chemical　use　calls　for　enhanced　pesticide　detection　to　safeguard　food　quality　and　public　health.　The　development　of　accurate　testing　methodologies　is　imperative　to　mitigate　the　environmental　impact　of　pesticides　and　ensure　the　integrity　of　ecosystems,　thereby　reflecting　the　pressing　need　for　advancements　in　agricultural　safety　protocols.　Therefore,　the　development　of　highly　sensitive　monitoring　technology　for　detecting　pesticide　residues　in　agricultural　products　is　necessary　for　safeguarding　human　health,　ensuring　food　safety,　and　maintaining　environmental　sustainability.　Results:　Herein,　a　controllable　surface　charge　on　single　tungsten　atom-modified　gold　nanoparticles　was　used　to　create　an　electrostatic　force　with　positively　charged　pesticide　residues.　Moreover,　hydrogen　bonds　formed　by　single-atom　sites　can　induce　analyte-adsorbed　nanoparticle　aggregation,　and　the　sizes　of　single-tungsten-atom-decorated　AuNPs　can　maintain　a　gap　between　each　other,　resulting　in　improved　SERS　detection　sensitivity　through　analyte　enrichment　at　gold　nanoparticle　hotspots.　In　terms　of　the　detection　limits　for　pesticide　residue　analysis,　we　can　effectively　achieve　an　ultrahigh　sensitivity　of　0.1　ppb　for　acetamiprid,　paraquat　and　carbendazim,　which　is　among　the　best　SERS　sensitivities　at　the　state　of　the　art.　For　apple　sample　analysis,　our　work　demonstrated　good　reproductivity　(RSD＜6　%)　and　a　strong　linear　relationship　(R-2　＞=　0.97)　for　4　pesticide　residues　after　optimizing　the　pretreatment　process,　which　proves　the　enormous　potential　in　quantitative　analysis.　Significance:　Single-atom　sites　hotspot　are　firstly　successfully　achieved　and　uniformly　dispersed　between　Au　nanoparticle,　which　can　effectively　increase　the　sensitivity,　keep　stability　of　the　Raman　scattering　signals　and　possess　a　significant　improvement　beyond　that　of　undecorated　hotspots　when　applied　in　pesticide　residue　detection.　This　method　can　be　employed　as　a　universal　strategy　to　capture　pesticide　residues　at　hotspots　for　SERS　detection.