Recently, stainless steel has been widely used as the solar cell substrate. In this paper, chemical mechanical polishing technique was employed to prepare the ultra-smooth 316L stainless steel surface for such application. The effects of solid content, pH, H 2 O 2 and benzotriazole (BTA) on the polishing performance of 316L stainless steel were investigated. The results indicated that, at pH 4.00, with the increase in the H 2 O 2 concentration, the MRR first dramatically increases due to the fact that, with the addition of small amount of H 2 O 2 , a porous outer layer mainly consisting of iron-enriched oxides with relatively low mechanical strength of the bilayer-structure oxide film is rapidly formed on the surface. After reaching the maximum value, the MRR gradually decreases since the outer layer gradually grows compact by the transformation of γ-FeOOH into α-FeOOH and even into α-Fe 2 O 3 . With the addition of BTA, the MRR can be suppressed, which is probably attributed to the formation of BTA passivating film on the top surface. Finally, a two-step polishing method was proposed, by which the ultra-smooth 316L stainless steel surface with the surface roughness R a about 2.0 nm can be achieved within 30 min and it can be subsequently used for thin-film solar cells.