Oxidation of starch with H2O2 was catalyzed by tungstate, metavanadate and copper-iron salts, respectively. The oxidation degree of oxidized starch and H2O2 decomposition rate were determined. The functional groups and molecular weight of oxidized starch were characterized by 13C-NMR, FT-IR and GPC. Then the tanning performance of oxidized starch-zirconium complexes was investigated. The hydroxyl groups on the C-2, C-3 and C-6 of glucose unit were oxidized to carbonyl and carboxyl groups, and the glycosidic bonds were broken during oxidation using cooper-iron salts as catalyst. This resulted in a relatively low molecular weight (14628) and a high oxidation degree (72.5%) of the oxidized starch. When it was used as a ligand of zirconium tanning agent, the Zr distribution (97.8%) and fixation (w(ZrO2)=8.0%) in leather were remarkably improved, and the shrinkage temperature of leather achieved 89.7℃, leading to better tanning performance. By comparison, tungstate catalyzed oxidized starch had a higher molecular weight (465095) and a lower oxidation degree (15.0%), and exhibited poorer tanning performance when coordinating with zirconium salt. The properties of metavanadate catalyzed oxidized starch was in between.