Co-incorporated alpha-FeOOH nanocrystal (Co-FeOOH) was synthesized and applied for the ozonation of atenolol (An) in water. The compound was characterized and recognized as a transitional structure from FeOOH to CoFeO4. The presence of Co-FeOOH was observed to support the formation of center dot OH by promoting ozone decomposition, and the degradation of ATL and TOC was significantly improved during the catalytic ozonation. Catalytic reactions were rationally designed in different water matrices, efficient and simultaneous removal of ATL and natural organic contaminants was achieved. It was found that the reactions kinetics depend strongly on the solution pH which could alter the surface properties of catalyst and influence the ozone-decomposition. Based on the 19 organic intermediates identified by IJPLC/Q-TOF-mass spectrometry, possible reaction pathways were accordingly proposed to elucidate the mechanism of atenolol degradation by ozone molecular and center dot OH. Three positions of ATL structure were concluded as the most vulnerable sites to be attacked by oxygen species to initiate the degradation path.