This work explores the adhesion properties of polymer solutions and thin coatings obtained by different‐composition poly(methylmethacrylate‐co‐n‐butylmethacrylate) copolymers. Surface wettability, work of adhesion, and work of spreading are calculated for solutions. Increasing amounts of n‐butylmethacrylate lead to higher values of work of adhesion, measured over two stent‐like flat surfaces (AISI 316L and pyrolytic carbon). The same moiety induces the solution viscosity increase and the decrease of the work of spreading and allows obtaining more homogeneous coatings. Adhesion of thin coatings is tested in dry (cross‐cut test) and wet (immersion) conditions. Adhesion tests of coatings obtained by solvent casting reflect thermodynamic parameters evaluated for solutions. Coatings show better strength in cross‐cut tests and a prolonged adhesion in wet conditions by raising the n‐butylmethacrylate fraction. The same trends are confirmed in commercial devices. In conclusion, the study of thermodynamic solution/substrate interactions can explain coating properties. The proposed approach is worthwhile to improve deposition procedures based on polymer solutions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47814.