In　this　paper,　shell-isolated　nanoparticle　enhanced　Raman　spectroscopy　(SHINERS)　has　been　applied　to　investigate　the　adsorption　of　typical　collectors,　butyl　xanthate　and　2-mercaptobenzothiazole　(MBT),　on　pyrite　surface.　With　the　help　of　inert　shell　isolated　gold　nanoparticles　as　electric　field　enhancers,　high　quality　electrochemical　spectra　were　obtained　in　relation　to　real-world　flotation　conditions,　enabling　the　quantitative　identification　of　the　chemical　reactions　occurring　only　on　the　mineral　surface.　It　has　been　found　that　polysulphide　anions　are　predominant　oxidation　product　of　pyrite　after　abrading　and　above　0　mV　vs　Ag/AgCl.　Both　the　adsorption　of　xanthate　and　MBT　are　suppressed　on　pre-oxidized　pyrite　surface.　The　pre-formed　polysulphide　is　diminished　at　negative　potentials,　which　are　favourable　for　collector＇s　adsorption.　Compared　to　xanthate,　MBT　shows　greater　resistance　to　pyrite　oxidation　and　a　broader　potential　window　for　adsorption　due　to　the　presence　of　two　＂minerophilic＂　groups　(endocyclic　nitrogen　atom　bonding　in　addition　to　the　interaction　through　the　exocyclic　S　atom).　Single　exocyclic　S　atom　bonding　is　predominant　in　more　favarouble　adsorption　environments.　Dithiolate,　the　oxidation　products　of　xanthate　and　MBT,　has　been　precluded　due　to　the　high　stability　of　adsorbed　collector.　This　is　inconsistent　with　the　ex-situ　XPS　measurement　where　air　exposure　may　induce　oxidation.