An insoluble thin film of a coronene diimide (CDI) derivative was fabricated from a soluble precursor of perylene diimide (PDI) by photoirradiation. We prepared a 1,7-diarylated PDI (TP-PDI) that can be converted into a coronene diimide (TP-CDI) derivative via a Scholl-type photocyclization reaction. This reaction was accompanied by structural changes from a twisted structure to a π-extended planar molecule. It was found that this photoconversion reaction occurs for both solution-based and thin-film-based reactants investigated by the changes of UV-vis absorption spectra and 1 H NMR spectra. The photocyclization reactions were found to proceed smoothly in polar solvents. In the thin-film state, the solvent vapor annealing method is a key process for achieving photoconversion reaction. Additionally, the fabrication of multi-layered thin films was achieved without undesirable dissolution of the underlying layers because of different solubilities of TP-PDI and TP-CDI.