The　development　of　advanced　Ni/Co-based　cathode　electrodes　for　aqueous　alkaline　Zn　batteries　(AZBs)　is　highly　desirable,　but　still　remains　a　challenging　task.　Herein,　we　rationally　design　and　synthesize　the　unique　MoSe2　decorated　Ni/Co　selenide　complex　hollow　arrayed　structures　(CH-MNCS)　with　dense　heterointerfaces　supported　on　nickel　foam　(NF)　through　a　metal–organic　framework-engaged　strategy,　in　which　heterostructured　CoSe/MoSe2　hollow　nanocages　are　uniformly　assembled　on　heterostructured　NiSex/MoSe2　nanotubes.　Benefiting　from　the　apparent　morphological,　structural　and　compositional　advantages,　aqueous　AZBs　based　on　the　NF/CH-MNCS　binder-free　cathode　exhibit　high　areal　capacity　and　energy　density　of　1.42　mAh　cm−2　and　2.45　mWh　cm−2　at　a　current　density　of　2　mA　cm−2,　respectively,　as　well　as　decent　rate　capability　and　long　cycling　stability.　Furthermore,　density　functional　theoretical　calculations　further　confirm　the　presence　of　heterointerfaces　can　not　only　enhance　the　electrical　conductivity　but　also　facilitate　the　adsorption　of　OH−　ions　in　the　electrolyte.　More　importantly,　the　quasi-solid-state　NF/CH-MNCS//Zn　batteries　are　also　assembled　to　demonstrate　the　potential　for　practical　applications.　This　work　may　provide　a　new　perspective　to　construct　heterostructured　transition　metal　selenide　complex　hollow　structures　on　conductive　substrate　for　aqueous　AZBs　and　other　energy　storage　devices.　©　2022　Elsevier　B.V.