The special surface appearance of complex surfaces restricts the coating film quality of spraying. The study of the atomization and film formation characteristics of typical complex surfaces, as well as the spraying mechanism, is essential for planning the spraying robotic trajectory and improving the spraying efficiency. In this paper, modeling and characteristics of the atomization and film formation process, based on CFD numerical simulations in previous studies, are systematically reviewed, focusing especially on airless spraying. In addition, the advantages and disadvantages of the existing research from the perspective of numerical models and methods are discussed. Finally, a further research direction for spraying on complex surface is prospected. Overall, a comprehensive and up-to-date review of spray atomization and film formation characteristics is considered valuable to practitioners and researchers in these fields, and will facilitate the further application of robotic spraying in the mechanical, automotive, marine, aerospace, petrochemical and other industries.