Although photolysis of antibiotics in aqueous solution was widely studied for a better understanding of their photolytic behavior in aqueous phase, the knowledge about photodegradation of antibiotics adsorbed on solid surfaces is still very limited. In this study, photodegradation of ciprofloxacin (CIP), a fluoroquinolone antibiotic, adsorbed in the intracrystalline space of montmorillonite (MMT) was examined using a xenon light source (300 W, lambda > 320 nm). The gradual decrease of basal spacing of MMT from 1.66 to 1.46 nm with irradiation confirmed CIP decomposition in the intracrystalline space under simulated solar irradiation. Nearly 70 percent of adsorbed CIP was degraded after 5 h irradiation, and the reaction followed the first-order kinetics with a rate constant roughly 3 times than that in aqueous solution, indicating more efficient photodegradation of CIP after being adsorbed in the intracrystalline space of MMT. Spectroscopic analysis revealed that direct photolysis was the main photolytic mechanism. The hydroxyl radical induced by irradiated MMT might play an important role. The major photoproducts were identified with liquid chromatography-tandem mass spectrometry, and the main degradation pathways were proposed. The results demonstrated that the photoproduct distribution and degradation pathways of CIP adsorbed in the intracrystalline space differed from those in aqueous solution.