The spatial orientation of chromophores defines the photophysical and optoelectronic properties of a material and serves as the main tunable parameter for tailoring functionality. Controlled assembly for achieving a predefined spatial orientation of chromophores is rather challenging. Metal–organic frameworks (MOFs) are an attractive platform for exploring the virtually unlimited chemical space of organic components and their self-assembly for device optimization. Here, we demonstrate the impact of interchromophore interactions on the photophysical properties of a surface-anchored MOF (SURMOF) based on 3,9-perylenedicarboxylicacid linkers. We predict the structural assembly of the perylene molecules in the MOF via robust periodic density functional theory calculations and discuss the impact of unit topology and π-π interaction patterns on spectroscopic and semiconducting properties of the MOF films. We explain the dual nature of excited states in the perylene MOF, where strong temperature-modulated excimer emission, enhanced by the formation of perylene J-aggregates, and low stable monomer emission are observed. We use band-like and hopping transport mechanisms to predict semiconducting properties of perylene SURMOF-2 films as a function of inter-linker interactions, demonstrating both p-type and n-type conduction mechanisms. ... mehrHole carrier mobility up to 7.34 cm2/Vs is predicted for the perylene SURMOF-2. The results show a promising pathway towards controlling excimer photophysics in a MOF while controlling charge carrier mobility on the basis of a predictive model.