Porous metal-organic frameworks (MOFs) have risen to their fame in material science in the past decades owing to their intrinsic porosities, diversified topologies, and tailored structures and properties, all of which are attractive for a wide spectrum of promising applications for gas storage/separation, greenhouse gas capture, catalysis and sensors, as well as newly established applications in membranes, thin film devices, and biomedical imaging. [1] MOFs as adsorbents, especially for H 2 , CO 2 , and volatile organic compounds (VOCs, typical hydrocarbons and alcohols, etc.) separation have attracted attention for energy and environmental technologies. Sterics (size/shape exclusion), thermodynamic equilibrium, as well as kinetic and quantum sieving effects are dominant factors in a separation process involving porous materials. Like other kinds of porous materials such as carbon, [2] zeolites, [3] and silica films, [4] MOFs provide interesting potential for selective adsorption and separation at the molecular level because of their pore structures and sizes which can be precisely controlled at the molecular level. [5] In principle, MOFs crystallized as anisotropic crystallographic systems should exhibit distinct adsorption kinetics for adsorbates approaching from different directions owing to varied pore openings. Nevertheless, most property studies of MOFs have dealt with nanoscale bulky powder or singlecrystal samples with randomly distributed crystallite orientations, which exhibits overall adsorption kinetics from all orientations. In contrast, the anisotropic nature of MOF crystals is averaged. One of the very few examples is the anisotropic [{Cu 2 (bza) 4 (pyz)} n ] (bza = benzoate; pyz = pyrazine) as a single-crystal membrane for gas separation, in which the aligned channels gave rise to a much higher permeance and permeation selectivity for H 2 and CO 2 than observed for the nonporous direction. [6] Nevertheless, this study on one single crystal may have limited importance for direct applications since it is challenging to grow large single crystals of MOFs. Advanced thin film/membrane technologies have been coupled with MOFs, and typical examples are ZIF-based membranes. [7] Such membranes displayed superior gas separation performance, and could provide an alternative way of using MOF materials in separation technologies. Although adsorption properties on some well-oriented MOF thin films/membranes have been reported, [8] to the best of our knowledge, no orientation-dependent adsorption on MOF thin films or homogenous ensembles of oriented MOF crystallites attached to surfaces (SURMOFs) has ever been studied.To investigate anisotropic properties, the first task was to prepare a MOF thin-film material, or better said, a homogeneous sample of MOF crystallites attached to a suitable surface with controlled, uniform orientation.Step-by-step liquid-phase epitaxy (LPE) is suited for this purpose, and involves the oriented growth of MOF nano-and microsized crystallites regulated by the functionality of self-...