The invention relates to a chemical polishing agent for stainless steel product surface polishing, a preparation method and a polishing method thereof. The chemical polishing agent is prepared by adding 13-20 g/L of ammonium bifluoride, 85-110 mL/L of nitric acid, 110-130 mL/L of phosphoric acid, 140-160 mL/L of hydrochloric acid, 20-30 g/L of sodium chloride, 85-95 mL/L of hydrogen peroxide, and 25-40 mL/L of a composite additive to water, wherein the composite additive contains 4-6 g/L of hexamethylenetetramine, 10-15 g/L of polyethylene glycol, 10-12 g/L of urea, 5-7 g/L of sulfosalicylic acid, and 4-8 g/L of an OP emulsifying agent. According to the present invention, surface flatness and glossiness of a stainless steel work-piece are increased, consumption of a large amount of electric energy is not required, chromic anhydride toxic substances are not generated, and waste water treatment requirements are reduced.