Sustainable　hydrogen　fuel　supply　through　electrochemical　water　splitting　requires　highly　efficient,　low-cost　and　robust　electrocatalysts.　Interface　engineering　is　of　key　importance　to　improve　the　catalytic　performance　in　a　heterogeneous　electrocatalytic　system.　Herein,　a　porous　microcubic　framework　composed　of　a　ZnO/ZnMoO4　heterostructure　(ZnO@ZnMoO4)　is　prepared　by　a　hybrid　zeolitic　imidazolate　framework-derived　oxidation　method,　and　it　shows　much　enhanced　hydrogen　evolution　reaction　(HER)　activity　in　alkaline　media.　The　overpotential　(at　10　mA　cm-2)　for　ZnO@ZnMoO4　is　significantly　reduced　by　30%　and　20%　compared　with　those　for　virgin　ZnO　(v-ZnO)　and　polycrystalline　zinc　molybdenum　oxide　(PZMO),　respectively.　The　enhanced　electrocatalytic　activity　should　be　attributed　to　the　ZnO/ZnMoO4　heterostructure,　which　can　synergistically　facilitate　the　charge　transport.　This　work　provides　a　more　structured　design　strategy　for　electrocatalysts　for　future　electrochemical　energy　conversion　systems.　©　2021　The　Royal　Society　of　Chemistry.