Duplex steel and cast steels have a wide range of applications in many industrial sectors, for example, oil extraction, printing, petrochemical industry, energy—exhaust gases desulphurization systems, seawater desalination plants, and the shipbuilding industry. The machine elements can be produced with different techniques, which determine the operational properties. A material with the same chemical composition made as a casting will have worse mechanical properties than, for example, a forged element. This depends on the microstructure, its fragmentation and its morphology. However, the costs of casting are lower than, for example, forging, and, in addition, not all shapes obtainable in the casting process can be made using metal–plastic working methods. This article presents research results concerning the influence of the burnishing process on the properties of the duplex cast steel surface layer. The purpose of the research was to verify the impact of static pressure roller burnishing (SPRB) parameters on the wear of the surface layer of duplex cast steel. The subject of the research was cast steel in the GX2CrNiMoN22-5-3 grade—according to PN-EN 10283:2019—that was burnished using 15 variants of technological parameters. Then, the samples were subjected to surface wear tests using the INSTRON 8874 device. On the basis of the observed wear appearances, the acting wear mechanisms are defined and evaluated according their contribution to the wear behavior. Detailed information about the wear phenomena will help industries to minimize their maintenance losses related to surface wear. The possibility of shaping surface properties by mechanical burnishing is part of the current direction of surface engineering development. This technology, combined with a high-potential material such as duplex cast steel, makes it possible to increase wear resistance.