Herein,　a　facile　assembly　strategy　and　ion　exchange　reaction　coupled　with　the　following　selenization　treatment　have　been　developed　for　the　synthesis　of　V-doped　transition　metal　nickel-cobalt　selenide　prism　with　hierarchical　yolk-shelled　structure　(named　as　VSe2-NiCoSex),　which　have　the　outer　shell　of　Ni-Co-VSe2　with　the　Ni-CoSe2　inner　core.　Notably,　VSe2-NiCoSex　presented　prominent　bifunctional　electrocatalytic　performances　and　excellent　conductivity　toward　both　dye-sensitized　solar　cells　(DSSCs)　and　hydrogen　evolution　reactions　(HERs)　for　water　electrolysis.　As　for　DSSCs,　VSe2-NiCoSex　electrode　exhibited　a　remarkable　power　conversion　efficiency　(PCE)　of　9.50%,　R-ct　of　1.09　Omega　and　E-pp　of　231　mV　than　that　of　Pt　(8.29%,　4.25　Omega　and　414　mV)　under　the　same　testing　conditions.　Besides,　VSe2-NiCoSex　as　HER　catalyst　delivers　a　lower　overpotential　of　84.3　mV　at　the　current　density　of　10　mA　cm(-2)　and　a　small　Tafel　slope　of　49.1　mV　dec(-1)　in　0.5　M　H2SO4.(c)　2023　Hydrogen　Energy　Publications　LLC.　Published　by　Elsevier　Ltd.　All　rights　reserved.