Herein, the surface of A473M martensitic stainless steel is strengthened by rolling processing technology. The microstructure evolution and plastic deformation behavior are characterized by electron backscatter diffraction (EBSD). The experimental results indicate that residual compressive stress will be formed on the surface of A473M steel after rolling, and the maximum value can reach 946 MPa. The surface roughness decreases significantly from 383 to 62.7 nm, which is only 1/5 of the matrix. The microstructure of the rolled samples is obviously refined, and <101>//ND texture is formed. The nanohardness of the hardened layer on the sample surface increases from 2.5 to 4.8 GPa, and the elastic modulus increases from 140 to 217 GPa. Compared with the matrix, the tensile strength and yield strength after rolling are increased by 40% and 22%, respectively. EBSD analysis indicates that the texture of the rolled samples after tensile changed from the <101>//TD direction of the matrix to the <101>//TD and <111>//RD directions.