Stellite 6 alloy has excellent wear resistance, corrosion resistance, and oxidation resistance, however the difficulties in traditional processing limit its wide application. Additive manufacturing technology that has emerged in recent years is expected to provide a new way for the processing of stellite 6 alloy. In this study, two square thin-walled stellite 6 parts were fabricated through the wire arc additive manufacturing technology. At the same time, the effect of stress relief annealing on the mechanical performance of the fabricated stellite 6 part was studied and compared with the corresponding casting part. The results indicate that the additive manufacturing stellite 6 components exhibit satisfactory quality and appearance. Moreover, the microstructure of the additive manufacturing part is much finer than that of the casting part. From the substrate to the top region of the additive manufacturing part, the morphology of the dendrites changes from columnar to equiaxed, and the hardness increases firstly and then decreases gradually. In addition, the average hardness of the additive manufacturing part is ~7–8 HRC higher than the casting part. The ultimate tensile strength and yield strength is ~150MPa higher than the casting part, while the elongation is almost the same. The stress relief annealing has no significant effect on the hardness of the AM part, but it can slightly improve the strength.