Based on the computational fluid dynamics (CFD) theory, this paper proposes a film formation model and a numerical simulation method that can be used in thickness prediction of airless spraying robots. The spraying flow field and the film formation process in the airless spraying process were simulated by the Eulerian–Eulerian approach, and the airless spraying film formation model including the paint expansion model and the wall hitting model was established. To verify the correctness of the model, numerical simulations of static spraying and dynamic spraying were carried out on the plane and arc surfaces. The simulation results showed that the width of the spraying flow field on the far wall increased linearly with the longitudinal distance in the major-axis direction. The busbar spraying on the outer surface of the arc surface showed the similar characteristics to the plane in the major-axis direction. Besides, the annular spraying was similar to the plane spraying in the minor-axis direction, but the inner surface spraying was completely opposite. When spraying the outer surface, the film thickness increased with the increase of the inner diameter but was smaller than that of the plane spraying, while the inner surface spraying was completely opposite. In the spraying experiment, the plane dynamic spraying and the arc plane inner and outer surface translation spraying were selected for verification. The experimental results were in good agreement with the simulation results, indicating that the film formation model of airless spraying established in this paper is basically correct. As a result, this model can be used for thickness prediction of spraying robots.