A series of phosphotung-based catalysts was synthesized by a impregnation method using silicone ball as the support．The supported catalysts were characterized by XRD，FT-IR，UV-Vis DRS．The catalytic behaviors of these catalysts in the oxidative reaction of maleic acid to DL-tartaric acid have also been investigated．The results indicated that tungsten could more effectively dispersed in the surface of the carrier after adding phosphate．The surface properties and oxidation catalyst performance were effectively adjusted by controlling charge number of PW. The supported catalyst had better catalytic reactivity when molar ratio of W/P was 1:2，Charge number was 30%，activation temperature was 400℃and activation time was 4h．The conversion rate of maleic acid was 96.5% and yield of DL-tartaric acid was up to 91% when the mass fraction of catalyst in mixed solution was 2.5%，reaction temperature was 70℃，reaction time was 3h，hydrolysis temperature was 105℃ and hydrolysis time was 3h．