In this work, poly(ethylene oxide) (PEO)–silica hybrid coatings were prepared by the sol–gel method and applied onto PC to improve its scratch resistance. The organic–inorganic hybrids were thermally cured into hard transparent coatings by using conventional and microwave (MW) ovens. Both techniques proved to be equally efficient in promoting the system’s crosslinking, as evaluated by 29Si MAS-NMR. The MW-assisted curing, however, was much faster. Instrumented scratch tests for the coated samples revealed an increase of 1 order of magnitude in the minimal load at which a scratch track appears on the sample surface. However, the friction coefficient values for samples with thermally cured coatings were lower than those produced by MW-assisted curing.