Electrocatalytic　nitrogen　reduction　reaction　(NRR)　is　a　sustainable　approach　for　NH3　production　with　low　energy　consumption.　However,　competing　hydrogen　reduction　reaction　(HER)　in　aqueous　solution　results　in　low　NH3　production　and　Faraday　efficiency　(FE).　Here,　MoS2　nanostructures　with　a　hydrophobic　surface　are　synthesized　by　alkyl　thiols　modification.　Aerophilic　and　hydrophobic　surface　facilitates　an　efficient　three-phase　contact　of　N-2,　H2O,　and　catalyst.　Thus,　localized　concentrated　N-2　molecules　can　overcome　the　mass　transfer　limitation　of　N-2　and　depress　the　HER　due　to　lowering　the　proton　contacts.　Although　the　active-sites　decrease　with　the　increase　of　the　alkyl　chain　since　the　thiol　may　cover　the　active　site,　the　optimized　electrocatalyst　achieves　NH　3　yield　of　12.86　x　10(-11)　mol.cm(-2).s(-1)　at　-0.25　V　and　22.23%　FE,　which　are　4.3　and　24　times　higher　than　those　of　MoS2-CP　electrocatalyst,　respectively.　The　increased　catalytic　performance　is　attributed　to　the　high　N-2　adsorption　and　depressed　HER.