Stainless steels with high mechanical properties and corrosion resistance are promising structural materials for the next generation of aerospace and some niche industries. In this work, we pre-formed a gradient nanostructured (GNS) surface layer on 316L stainless steel by surface mechanical rolling treatment (SMRT) and subsequently annealed it at 700 °C. Tensile tests showed that the strength-ductility synergy was enhanced in the annealed-SMRT sample, while the grain size and hardness in the GNS layer retained rather stable. In addition, a remarkable Cr-enrichment was found in the GNS surface layer after annealing, resulting in a significantly enhanced corrosion resistance. The underlying mechanisms on the microstructure, composition and phases evolutions, as well as their effects on deformation and corrosion behavior, were analyzed in the annealed-SMRT sample. This work provides insights on developing a simple thermomechanical approach to produce stainless steels with enhanced mechanical properties and corrosion resistance.