Nanoporous metal-organic frameworks (MOFs) are intensively investigated with respect to various applications such as in gas storage, in molecular separation and as sensors. In all these applications, the interaction with the guest molecules in the nanopores, as well as the diffusion properties, are crucial. In this topical review, thin MOF films, referred to as surface-mounted MOFs (SURMOFs), are discussed as a well-defined model system for detailed mass transfer studies. The origins of mass transport hindering surface barriers, which often slow down the mass transfer tremendously, and the slow diffusion of large molecules, are investigated by using thin MOF films. Another focus of this topical review is on photoswitchable MOF films. Azobenzene side groups in the MOF structure allow a remote control of the adsorption and diffusion properties. This is employed for demonstrating the remote-controlled release from a nanoporous container as well as for membrane separation where the separation factor can be continuously tuned by light irradiation.