In the automated spraying workshop of ship segments, poor visibility caused by dust and fog hampers the effectiveness of the video monitoring system. The traditional method used during the automated spraying process fails to provide real-time measurement of film thickness and prediction of spraying quality, resulting in uneven film thickness and high rework rates. Robotic spraying technology also faces challenges, such as the time-consuming and labor-intensive process of building and computing a highly reliable Computational Fluid Dynamics (CFD) based spraying film-forming simulation model, which cannot be reflected in real-time during the spraying process. The digital twin characterization method, based on the agent model, offers a solution to these limitations and challenges, providing new ideas and approaches for improving and optimizing the spray film formation model. This paper presents the development of a real-time characterization system for sprayed film thickness based on digital twin technology. The spraying film thickness under different working conditions is obtained using Ansys-Fluent simulation software by varying the gun height and gun speed. The predictive model for spraying film thickness is then established using the obtained simulation data and the corresponding gun height and gun speed, employing the surrogate modeling method (BP neural network). The real-time characterization system for spraying film thickness is developed by combining C# and Unity3D. Finally, in order to ensure the accuracy of the predictive model, a spraying experimental platform is built to verify the accuracy of the predictive model.