Electrospinning　is　a　prominent　technique　for　fabricating　polymer-stabilized　composite　nanofibers　for　surface-enhanced　Raman　scattering　(SERS).　However,　further　exploration　of　the　surface　chemistry　of　these　electrospun　composite　substrates　is　crucial　to　manipulate　the　charge　transfer　(CT)　effect　and　achieve　synergistic　effects　between　CT　and　localized　surface　plasmon　resonance　(LSPR)　for　enhanced　bio-labeling　and　pesticide　detection.　Here,　we　present　the　development　of　a　flexible　and　self-supporting　SERS　substrate　using　electrospinning,　consisting　of　polymer-coated　silver　nanowires　(AgNWs).　By　employing　different　polymer　shells　and　probe　molecules,　we　strategically　adjusted　the　energy　levels　of　the　frontier　orbitals,　enabling　effective　control　over　the　CT　effect.　The　resulting　nanofibers　exhibited　optimized　selectivity　and　sensitivity　through　multiple　CT　routes,　enabling　the　detection　of　thiram　in　apple　skin　using　a　convenient　wiping　sampling　method　with　a　low　limit　of　detection　(LOD)　of　5　ng/cm².　We　also　investigated　other　pesticides　without　viable　CT　routes　to　demonstrate　the　versatility　of　the　composite　substrates,　although　they　exhibited　relatively　lower　selectivity　and　sensitivity　due　to　the　absence　of　synergistic　effects.　This　study　highlights　the　potential　of　CT　manipulation　in　harnessing　synergistic　effects　in　electrospun　2D　composite　nanofibers,　thereby　advancing　the　practical　applications　of　SERS　technology.　©　2023　Elsevier　B.V.