A series of dimethyldihydropyrene (DHP)-pyridyl photochromic derivatives has been synthesized and its photochemical behaviour characterized by spectroscopic and electrochemical methods. The corresponding noncovalently-linked electron donor–acceptor complexes have been isolated. They combine the DHP-pyridyl ligand as a donor and the zinc(II) tetraphenylporphyrin as acceptor. Such association allowed to explore the efficiency of dative bonds to monitor the interactions between the two units.