In order to obtain tungsten with great surface qualities and high polishing efficiency, a novel method of chemical enhanced shear dilatancy polishing (C-SDP) was proposed. The effects of pH values and H2O2 concentrations on the polishing performance of tungsten C-SDP were studied. In addition, the corrosion behaviors of tungsten in solutions with different pH values and H2O2 concentrations were analyzed by electrochemical experiments, and the valence states of elements on the tungsten surface were analyzed by XPS. The results showed that both pH values and H2O2 concentrations had significant effects on tungsten C-SDP. With the pH values increasing from 7 to 12, the MRR increased from 6.69 µm/h to 13.67 µm/h. The optimal surface quality was obtained at pH = 9, the surface roughness (Ra) reached 2.35 nm, and the corresponding MRR was 9.71 µm/h. The MRR increased from 9.71 µm/h to 34.95 µm/h with the H2O2 concentrations increasing from 0 to 2 vol.%. When the concentration of H2O2 was 1 vol.%, the Ra of tungsten reached the lowest value, which was 1.87 nm, and the MRR was 26.46 µm/h. This reveals that C-SDP technology is a novel ultra-precision machining method that can achieve great surface qualities and polishing efficiency of tungsten.