Depolymerization of lignin to low-molecular-weight products plays a vital role in upgrading of lignin into high value chemicals. One of the problems of lignin depolymerization is the recondensation of the lignin fragments through positive a carbon (C-alpha(+)) coupled with electron-rich lignin aromatic rings during the depolymerization process. Many pretreatment methods have been proposed to efficiently inhibit the recondensation by blocking active C-alpha-OH groups, but barely a few oxidative methods were reported for the following lignin depolymerization. Herein, we reported an effective lignin depolymerization process in which the active C-alpha-OH groups were first converted to stable C-alpha=O by TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) and then depolymerized by oxidation of polyoxometalate (POM) under relatively mild conditions (150 degrees C, 10 bar O-2). The POM is an intermediate oxidation agent that was completely regenerated during the lignin depolymerization process. Under 150 degrees C and 10 bar O-2 for 6 h, 74.5 wt % lignin was converted to DCM-extractable low molecular-weight compounds (average molecular weight of 363 Da), yielding 19.4 wt % aromatic monomers (based on total lignin mass). The novel oxidative depolymerization method reported here is more effective than common oxidative depolymerization methods reported in the literature.