Zirconia ceramics and carbon-based materials are widely adopted in medical and dental applications due to their excellent biocompatibility and aesthetics. However, fracture toughness of ceramic materials limits their application in clinical dentistry because of the existence of residual stress. In this study, zirconia/graphene oxide (ZrO2-GO) composite ceramics were fabricated by hot-press sintering. Residual stresses developed on the surface of ZrO2-GO composite ceramics were evaluated by X-ray residual stress analysis and indentation techniques. The variation of surface residual stress with GO content was evaluated, and found to be consistent with that of fracture toughness. The generation of residual stress was found to be directly related to fracture toughness. Residual stress calculated by theoretical formula of indentation method was consistent with that measured by X-ray diffraction in line with the content of GO. Based on above results, it is concluded that 0.1–0.15 wt% GO composite ceramics possessed better mechanical properties.