The dependence of adhesion of four various UV-curable protective coatings of optical fibers to the surface of fused silica on the time of UV irradiation was investigated. The maxima of adhesion were observed in short periods of time of curing. Comparison of adhesion values to the hardness, gel content, and contact angles of water measured on the polymer surface revealed that adhesion of epoxyacrylate protective coatings of optical fibers depended on the inner structure of the polymer rather than on its surface properties. This observation was confirmed by IR studies.