The applications of three-dimensional superstructures that consist of metal-organic framework (MOF) crystals are promising, but limited by spatial control over the crystallization process. Here a hydrophobic hierarchical metal-organic framework (HZIF-8) containing unusual micro-, meso-, and macropores was designed and synthesized by a template strategy, in which the polystyrene (PS) not only acted as the template to construct the macropores, but also modified the hydrophilic crystal surface of ZIF-8. When used as adsorbent for liquid oil/water separation, HZIF-8 demonstrated significantly enhanced oil adsorption performance while maintaining very low water uptake.