Molybdenum　disulfide　is　regarded　as　the　inheritor　of　Pt-based　catalysts　for　the　hydrogen　evolution　reaction　(HER),　arising　from　low-cost　and　abundant　resource.　However,　the　electrocatalytic　efficiency　of　MoS2　is　much　lower　than　that　of　Pt-based　catalysts,　as　a　result　of　lacking　edge　active　sites,　poor　activity　of　basal　plane,　and　deficient　conductivity.　Herein,　by　introducing　nanoflower-like　MoS2　with　PVP　coating　(PVP@MoS2)　as　catalyst,　high　performance　for　HER　is　observed.　The　higher　efficiency　of　PVP@MoS2　is　mainly　due　to　the　four　points:　(1)　the　formation　of　more　spatial　manipulated　nanoflower　structure　by　thin　MoS2　slices　exposing　large　amount　of　edge　active　sites;　(2)　improving　basal　plane　atom　utilization　with　the　enlarged　(002)　plane　from　6.2　to　6.8 Å;　(3)　the　intrinsic　conductivity　of　MoS2　increases,　because　the　electron　can　transfer　from　C=O　and　C–N　to　MoS2;　(4)　the　decreased　hydrogen　atom　absorption　energy　from　0.815　to　0.684 eV　extracts　from　DFT　calculation.　Therefore,　the　synergetic　effect　of　the　micro/nano-structure　and　electronic　structure　offers　a　simple,　effective,　and　possible　way　for　many　other　2D　materials　to　enhance　their　electrocatalytic　HER　activity.　[Figure　not　available:　see　fulltext.].　©　2020,　Springer　Science+Business　Media,　LLC,　part　of　Springer　Nature.