An important challenge faced by the automotive industry is the phenomenon known as overspray, which occurs when excess paint particles are dispersed beyond the target surface and contaminate the surrounding environment. This issue is particularly critical in automated painting lines, where painting robots are continuously exposed to overspray. To mitigate potential damage, these robots are commonly protected with polyester covers. However, due to the intrinsically hydrophilic nature of polyester, paint particles are readily absorbed by the fabric, resulting in frequent cover replacement, increased downtime, and significant waste generation. A promising strategy to overcome this limitation is the development of superhydrophobic protective covers. On superhydrophobic surfaces, liquid droplets adopt an almost spherical shape and roll off easily, minimizing their contact with the surface. When applied to painting environments, this behavior is expected to reduce paint adhesion and absorption, thereby enhancing the durability and service life of protective covers. In this work, several surface modification strategies were investigated to impart polyester fabrics with highly hydrophobic and near-superhydrophobic properties. These approaches involved the incorporation of nanomaterials, namely, silica and alumina nanoparticles, to introduce hierarchical micro- and nanoscale surface roughness. In addition, low surface free energy compounds, specifically stearic acid and hexadecyltrimethoxysilane, were applied to further enhance hydrophobicity. The results demonstrated that the immobilization of polyester fabrics with nanomaterials alone led to an increase in the water contact angle; however, water droplets remained pinned to the surface and did not readily roll off. These hydrophobic features were attributed to the increased roughness of the fibers, as confirmed by means of scanning electron microscopy and surface roughness measurements. When nanomaterials were combined with hydrophobic agents, a synergistic effect was observed, resulting in both higher water contact angles and significantly reduced sliding angles.