Transition　metal　selenide　composites　with　a　core-shell　structure　offer　a　compelling　alternative　to　platinum-based　catalysts　due　to　their　large　specific　surface　area,　abundant　edge　sites,　and　exceptional　synergy　between　the　core　and　shell　components.　Core-shell　selenide　microspheres　were　prepared　using　bismuth　bromide　oxide　(BiOBr)　as　the　core　and　covered　with　a　Ni-Co　layered　double　hydroxides　(LDH)　shell　transferred　from　ZIF-67　through　a　simple　capping　process.　After　selenization,　this　formed　core-shell　structure　has　an　inner　core　of　Bi2Se3　supporting　a　NiSe2/CoSe2　shell　(denoted　as　Bi2Se3@CoSe2/NiSe2).　The　remarkable　ability　of　Bi2Se3@NiSe2/CoSe2　to　efficiently　transfer　electrons　for　iodide　and　H+　allows　it　to　achieve　exceptional　photovoltaic　conversion　efficiency　as　a　counter　electrode　(CE)　in　dye-sensitized　solar　cells　(DSSCs)　and　demonstrate　strong　performance　in　the　hydrogen　evolution　reactions　(HERs).　The　power　conversion　efficiency　(PCE)　of　Bi2Se3@NiSe2/CoSe2　electrocatalysts　in　DSSCs　is　9.39%,　significantly　higher　than　that　of　Pt　(6.89%).　Besides,　during　alkaline　HER　(1.0　M　KOH),　Bi2Se3@CoSe2/NiSe2　has　a　lower　onset　potential　of　35.5　mV　and　a　smaller　Tafel　slope　of　58.9　mV　dec-1　.　This　work　provides　a　new　approach　to　the　design　of　cost-effective　and　efficient　core-shell　micromaterials,　which　can　be　applied　to　the　synthesis　of　other　Pt-free　electrocatalysts.