The work aims to predict surface residual stress during forming process of high velocity arc spraying by proposing a new prediction model made up of continuous thermal mismatch stress and curvature quenching stress for surface residual stress on coatings. Models of continuous thermal mismatch stress and quenching stress curvation were established, respectively, based on force and moment equilibrium principle as well as overlapping coating hypothesis. Numerical model of residual stress on the sprayed surfaces was obtained after these models were combined. Comparing the predicted values with measured residual stresses on the sprayed surfaces by XRD indicated that, surface residual stress of the coating after one time spraying was the maximum during coating formation process. Varying pattern of surface residual stress differed as coating thickness was nearly 500 μm, i.e., both theoretical predicted values and measured values firstly decreased as spraying thickness increased. As the spraying thickness of coatings deposited up to 500 μm, the theoretical results were subject to stationary fluctuation while measured value increased to 1500 μm and decreased gradually. This new prediction model can accurately predict the maximum residual stress and residual stress of thicker coatings with thicknesses less than 500 μm. The distribution law of residual stress on the formed coating surface is revealed, i.e., the residual stress first decreases and then increases slightly as it deposited to 500 μm as depositing thicknesses of the coating increased.