The structural property of phenolic and non-phenolic lignin has an effect on the reaction rate of lignin by oxygen and chlorine dioxide respectively. Moreover, the undesirable degradation of cellulose followed by lignin degradation is influenced by chemical charge and reaction time. In this paper, several lignin model compounds were used to illuminate the interaction of oxygen and chlorine dioxide by varying the position of O and D(OD, DO, ODO and DOD), and gas chromatography method was used to investigate the degradation of lignin by determining the content of methoxyl groups in lignin. It was shown that structural properties of lignin models were more influential on the degradation and demethylation of lignin than the above combination. Combination of oxygen and chlorine dioxide, however, was more effective in degradation of lignin than only one stage, and three stages than two stages.