Wettability of electrospun fibers is one of the key parameters in the biomedical and filtration industry. Within this comprehensive study of contact angles on three-dimensional (3D) meshes made of electrospun fibers and films, from seven types of polymers, we clearly indicated the importance of roughness analysis. Surface chemistry was analyzed with X-ray photoelectron microscopy (XPS) and it showed no significant difference between fibers and films, confirming that the hydrophobic properties of the surfaces can be enhanced by just roughness without any chemical treatment. The surface geometry was determining factor in wetting contact angle analysis on electrospun meshes. We noted that it was very important how the geometry of electrospun surfaces was validated. The commonly used fiber diameter was not necessarily a convincing parameter unless it was correlated with the surface roughness or fraction of fibers or pores. Importantly, this study provides the guidelines to verify the surface free energy decrease with the fiber fraction for the meshes, to validate the changes in wetting contact angles. Eventually, the analysis suggested that meshes could maintain the entrapped air between fibers, decreasing surface free energies for polymers, which increased the contact angle for liquids with surface tension above the critical Wenzel level to maintain the Cassie-Baxter regime for hydrophobic surfaces.