A coating with anti-fog properties was developed for a polycarbonate (PC) substrate using a multi-step process. A silicon-containing multilayer was first deposited by atmospheric pressure Townsend discharge (APTD) using hexamethyldisiloxane (HMDSO) precursor to ensure cohesion between the coating and the PC and to protect the polymer against dissolution in solvents during subsequent spin-coating processes. The multilayer was also developed in a nitrogen environment in order to provide amino groups on the surface, which allowed for the subsequent covalent bonding of the anti-fog layer. This anti-fog layer was made of a spin-coated (poly(ethylene-maleic anhydride) (PEMA) layer, used as a linking arm, followed by a spin-coated poly(vinyl alcohol) (PVA) layer, for its anti-fog properties. Surface analyses (XPS, FTIR, and AFM) confirmed that the silicon-containing multilayer was successfully deposited with a good control obtained for each step. The anti-fog coating, also tested with promising results, displayed a negligible loss of optical transmission across the visible spectrum.