Inter-　and　intra-molecular　hydrogen　bonding　plays　important　role　in　determining　molecular　structure,　physical　and　chemical　properties,　which　may　be　easily　ignored　for　molecules　with　a　non-typical　hydrogen　bonding　structure.　We　demonstrated　in　this　paper　that　the　hydrogen　bonding　is　responsible　for　the　different　Raman　spectra　in　solid　and　solution　states　of　p-Nitrothiophenol　(PNTP).　The　consistence　of　the　theoretical　calculation　and　experiment　reveals　that　the　intermolecular　hydrogen　bonding　yields　an　octatomic　ring　structure　R-2(2)　(8)　of　PNTP　in　the　solid　state,　confirmed　by　the　characteristic　S-H---O　stretching　vibration　mode　at　2550　cm(-1);　when　it　comes　to　the　solution　state,　the　breakage　of　hydrogen　bond　of　S-H---O　induced　the　S-H　stretching　vibration　at　2590　cm(-1).　Our　findings　may　provide　a　simple　and　fast　method　for　identifying　the　intermolecular　hydrogen　bonding.