This work aims at developing polymer surfaces with enhanced hydrophobicity by controlling both the surface chemistry and the surface structure. As a first step, a chemical surface modification is achieved by the incorporation of a synthetized tailored fluorinated copolymer, named POISE-a (Polymer prOcessing Interface StabilizEr), in a commercial polystyrene matrix. Then, a complementary physical approach based on micro-structuration of a polymer surface is used. Polystyrene films containing various contents of POISE-a were elaborated by a solvent casting method. The structuration of the films was conducted by replicating a texture from a nickel insert using a hot-embossing technique with optimized processing conditions. The beneficial effect of POISE-a on both the wettability properties and the replication efficiency was evaluated by the water/polymer static contact angle and the quantification of the replication rate, respectively. The use of this tailored additive, even at low percentages (i.e., 1 wt.%), associated with the structuration of the PS surface, improves both the hydrophobicity of polystyrene and the robustness of the replication process.