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　(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.　©　The　Author(s)　2016.