A　series　of　novel　cage-like　transition-metal　(TM)　incorporated　heteropolyoxoniobates　{TM4Nb64O200}　(1-TM,　TM　=　Ni,　Cu,　Mn,　Cd)　were　hydrothermally　synthesized　and　isolated　as　salts　of　mixed　K+　and　[CN3H6]+.　As　a　result　of　transition　metal　ions　incorporation,　the　charge　distribution,　redox　potential,　and　active　sites　of　the　formed　polyoxoniobates　(PONbs)　are　variants,　leading　to　differences　in　their　electrocatalytic　hydrogen　evolution　reaction　(HER).　Among　these　compounds,　1-Ni　showed　the　best　HER　activity　with　an　overpotential　of　560　mV　at　10　mA　cm-2　and　a　minimum　Tafel　slope　of　405.8　mV　dec-1.