Metal-organic frameworks (MOFs) provide a novel strategy to precisely control the alignment of molecules to enhance exciton diffusion for high-performance organic semiconductors. In this paper, we characterize exciton dynamics in highly ordered and crystalline porphyrin MOF nanofilms by time-resolved photoluminescence and femtosecond-resolved transient absorption spectroscopy. Results suggest that porphyrin MOF nanofilms could be a promising candidate for high-performance organic photovoltaic semiconductors in which the diffusion coefficient and diffusion length of excitons are 9.0 × 10 cm s and 16.6 nm, respectively, comparable with or even beyond that of other excellent organic semiconductors. Moreover, by monitoring real-time exciton dynamics it is revealed that excitons in MOF nanofilms undergo high-efficient intermolecular hopping and multiexciton annihilation due to the short intermolecular distance and aligned molecular orientation in MOF structure, thus providing new insights into the underlying physics of exciton dynamics and many-body interaction in molecular assembled systems.