A special polishing fluid suitable for atomizing polishing of TC4 titanium alloy was prepared. The smooth surface of titanium alloy at nanometer level was obtained through polishing experiments. The effects of different content of abrasives, oxidants and complexing agents on the removal rate and surface roughness of titanium alloy materials were studied. The composition and proportion of polishing solution were optimized by orthogonal experiment.The optimized polishing solution consists of 20% SiO2 abrasive,0.1% citric acid,1% polyethylene glycol-400, and 2% H2O2, with a pH value of 4.The polishing test results show that the optimized polishing solution has a good polishing effect,which improves the material removal rate and the surface quality of the specimen,reaches the material removal rate of 549.87 nm/min and the surface roughness of 0.678 nm.XPS analysis results support that the titanium alloy surface reacts with H2O2 and citric acid in an acidic environment during polishing,forming an oxide layer that is easy to be removed by mechanical action.