Due　to　the　difficulty　of　developing　noble　materials　for　large-scale　applications,　transition　metal　oxide　materials　have　become　popular　alternatives　for　the　hydrogen　evolution　reaction.　However,　compared　to　commercial　Pt/C,　poor　conductivity　and　hydrogen　evolution　activity　are　common　for　transition　metal　oxides,　including　WO3-x-based　semiconductors,　so　it　is　therefore　necessary　to　ameliorate　the　electrode　self-properties　to　be　suitable　for　H2　production.　Here,　different　ratios　of　S2-　and　Ni2+　salts　are　introduced　into　hexagonal　WO3　and　Ni0.4WO3-xSx　is　prepared　successfully　after　oxygen　vacancies　and　W–O–S　and　Ni–W-O　bonds　are　formed　on　the　surface　of　the　Ni0.4WO3-xSx　nanorods.　The　X-ray　photoelectron,　Raman　and　electrochemical　impedance　spectroscopy　results　show　that　the　incorporation　of　Ni　and　S　atoms　can　increase　the　number　of　oxygen　vacancies　and　the　conductivity　for　hydrogen　evolution,　simultaneously　demonstrating　that　the　W–O–S　and　Ni–W–O　bonds　are　the　main　active　sites　of　the　Ni0.4WO3-xSx　nanorods.　Density　functional　theory　calculations　further　indicate　that　the　ΔGH*　of　NiWO3-xSx　is　closer　to　20　%　commercial　Pt/C.　The　Tafel　slope　reduces　to　87.3　mV/dec　when　approaching　the　Volmer–Heyrovsky　kinetic　mechanism　reaction.　Finally,　the　onset　potential　is　53　mV.　The　overpotential　is　173　mV　at　10　mA/cm2,　which　is　68　%　lower　compared　to　hexagonal　WO3.　©　2023　Elsevier　B.V.