An enzyme-like TiO(2)/reduced graphene oxide (enzyme-TiO(2)/rGO) nanocomposite with molecular recognition ability was fabricated by biomimicking the geometrical and chemical complementation of the enzyme and substrate. The anatase TiO(2) nanocrystals were densely dispersed on rGO nanosheets with close interfacial contacts. With geometrical and chemical matching of target molecules and memorized cavities, the adsorption capacity of enzyme-TiO(2)/rGO nanocomposites for 4-nitrophenol (4.71 mg g(-1)) is about six times that of control TiO(2)/rGO without the enzyme-like feature (0.79 mg g(-1)), and the enzyme-TiO(2)/rGO shows a relative selectivity coefficient of 7.24. Moreover, enzyme-TiO(2)/rGO exhibits molecular recognitive photocatalytic degradation for a particular contaminant. The results demonstrate that enzyme-substrate recognition provides a convenient and powerful basis on which to biomimic and construct efficient photocatalysts with high selectivity.