The benzene conversion and phenol selectivity from C6H6/O2/H2O over [Ca24Al28O64]4+4O(C12A7-O) catalyst were investigated using a flow reactor. The benzene conversion increases with the increase of temperature, and the phenol selectivity mainly depends on both reaction temperature and the composition of the mixtures. The changes of the catalyst structure before and after the reactions and the intermediates on the catalyst surface and in the bulk were investigated by XRD, EPR and FT-IR. The catalytic reactions do not cause any damage to the structure of the positively charged lattice framework C12A7-O, but part of the O and O2 species in the bulk of C12A7-O translate to OH after the reactions. The neutral species and anion intermediate were investigated by Q-MS and TOF-MS respectively. It is suggested that the active O and OH species played a key role in the process of phenol formation.