This study presents the contact angle prediction model of a trapezoidal groove structure based on the laser irradiation on polymethyl methacrylate (PMMA). The trapezoidal groove structure was designed and proposed according to the characteristics of a femtosecond laser. First, the complete wetting model and incomplete wetting model which were compatible with the characteristics of the laser mechanism were constructed based on the Gibbs free energy and the structural parameters of the trapezoidal groove structure. Then, based on the contact angle prediction models constructed, the samples were divided into two groups according to the designed structural parameters, and the experimental investigations were carried out. The result demonstrated that the incomplete wetting prediction model was more in line with the actual situation. The convex width and the top edge length of spacing of the trapezoidal groove structure both affected the contact angle prediction results. From both the experimental contact angles and the contact angles predicted by the incomplete wetting model, it could be known that the contact angle reached 138.09 • when the ratio of the convex width to the top edge length of spacing was 0.25, indicating that the smaller the ratio of the convex width to the top edge length of spacing, the better the hydrophobicity of PMMA.