Two‐step process that allows controlling independently roughness and chemical composition of plasma polymers, i.e., two parameters determining the wettability of such materials, is presented. In the first step a film composed of Ti nano‐clusters is deposited on a smooth substrate. Nano‐cluster films of different roughness can be obtained depending on deposition time. In the second step the nano‐cluster films are overlaid by a thin layer of plasma polymer having the desired chemical structure. This approach allows the tuning of wettability of the deposited films to as much as 50% of the wettability of the films having the same chemical structure but deposited on a smooth substrate.