At low Na2CO3 concentration the micelle–water interface of CPC micelle saturated with C6H5O−, and benzene ring penetrated into the palisade layer of CPC micelle, but deeper penetration was not observed with the increase of Na2CO3 concentration. Excessive CO32− could make some C6H5O− transfer from CPC micelle to water, resulting in the decrease of the solubilization extent of phenol in CPC micelle.