Oxidative coupling reaction of phenol mediated by birnessite was studied in aqueous phase and soil. Phenol was readily transformed by birnessite and almost all phenol disappeared in both samples after 24 hours of reaction. Phenol transformation kinetics was investigated by plotting reaction time against logarithm concentrations of residual phenol, revealing that exponential decrease of phenol was evident both in aqueous phase and soil, and maximum removal rates were 2.31-2.54 times higher in the presence of soil. Reaction products of phenol were identified by LC-MS and capillary electrophoresis. In aqueous phase, polyphenols were formed by self-coupling reaction of phenoxy radicals whereas phenol was found to be present as bound residues in soil, probably due to the cross-coupling reaction between the radicals and soil organic matter. Microtox System was employed to determine the toxicity after birnessite treatment, and the toxicity of phenol-spiked solution and soil samples decreased remarkably compared to that of phenol solution before treatment.