The powders of NiCrW and NiCrWRE alloys were flame sprayed on a medium-carbon steel substrate by thermal spray welding. The microstructure and tribological behavior of coatings were studied experimentally by means of scanning electron microscopy (SEM), field emission gun scanning electron microscope (FEGSEM), and wear tests. The addition of CeO2 modifies the coating morphology from a needle-like structure to a roughly cubic morphology; the refining and purifying effect of rare earth elements makes the microstructure more compact and finer. Analysis of the w surfaces reveals that the coatings with CeO2 addition show improved abrasive wear resistance over those without CeO2. By adding CeO2, the hardness of the coatings is significantly increased, and the wear resistance of the coatings is enhanced.