Rolling process based on the plastic deformation as a surface strengthening treatment was employed, aiming to improve the wear resistance ability and functional performance of the high carbon equivalent gray cast iron (HCEGCI). The microstructures and tribological performance of the untreated and rolled samples were characterized. In addition, the wear mechanism of HCEGCI samples was also studied via pin-on-disc tests. The experimental results show that the as-rolled samples possess the structure-refined layer of 15 μm and work-hardened layer of 0.13 mm. In comparison with the surface hardness of untreated samples, the surface hardness of as-rolled samples increases by 84.6% (from 240HV0.1 to 443HV0.1) and the residual compressive stresses existed within the range of 0.2 mm. The wear rates of as-rolled samples were decreased by 38.4%, 37.5%, and 44.4% under different loads of 5 N, 10 N, and 15 N, respectively. The wear characteristics of the untreated samples mainly exhibit the peeling wear coupled with partial adhesive and abrasive wear. However, as for the as-rolled samples, the adhesive wear was limited by the structure-refined layer and the micro-crack propagation was controlled by the work-hardened layer. Therefore, the wear resistance of as-rolled samples can be improved significantly due to the low wearing degree of the friction contact zone.