In this study, 1-hydroxypyrene (1-OHP)-imprinted TiO 2 gel films were prepared by spin coating. Incorporation of the template molecules and their removal were confirmed by UV–vis absorption spectra measurements. Guest selectivity of the 1-OHP-imprinted TiO 2 film was estimated to be 1.6, 1.9, and 1.4 against benzoic acid (BA), 1-naphthol (1-NA), and 4-(phenylazo)benzoic acid (4-PABA)-imprinted TiO 2 film, respectively. The 1-OHP-imprinted films demonstrated greater binding to 1-OHP than the reference imprinted films. Similar results were obtained with the BA, 1-NA, and 4-PABA-imprinted films, and their guest selectivity against the reference imprinted films amounted to 1.2–3.1 times greater. This result suggests that the binding cavity of the imprinted TiO 2 gel matrices discriminates between molecular size, shape, and functional groups. Although much improvement is still needed, this imprinting process is a simple, useful, and less time-consuming way to prepare discriminative receptor cavities.