A highly (111) oriented CuI/-cyclodextrin inorganic/organic composite film on glass substrates was deposited from a dispersion of CuI and beta-cyclodextrin in a mixture of acetonitrile and dimethylformamide (DMF) solvents, in which DMF plays an important role in the orientation of CuI film. The composite film exhibits obviously improved band gap photoluminescence compared with that of the pure CuI film due to the passivation of iodine-related defect sites by beta-cyclodextrin matrix. This result indicates that the optical properties of CuI film can be easily adjusted by the formation of composite film with proper ligand agents.