Surfaces with translucent and wear-resistant effects have a wide range of applications, especially as protective layers. In this work, a simple and convenient method for the preparation of porous magnesium fluoride (MgF2) coatings was proposed. Nano-porous MgF2 powder was prepared with sol–gel and phase separation methods by optimizing the polymer amount and used for the preparation of thick layers onto PVC substrates. The automated surface area and porosity analyzer (BET) and scanning electron microscopy (SEM) confirmed that the layers containing 0.028‰ PEO presented a 3D structure with pore sizes in the range of 16 nm. The layer reached 93% transmittance in the visible region, a Vickers hardness value of 2889.1 kg/mm2, and a friction coefficient of 0.2 in the wear test.