Abstract: The invention disclosed includes a coating composition for siliceous surfaces. The coating includes at least one component from the group consisting of poly(alkoxy)silane, poly(halo)silane, alkoxysilane, halosilane, and mixtures thereof and a catalyst compound which generates a proton to hydrolyze the component when exposed to radiation. Preferably, the catalyst is a photo-acid. The invention also includes a method of coating the optical fiber. The aforementioned coating is applied to an exterior surface of the fiber. A proton is generated to promote the hydrolysis of the component. The invention further includes a method of accelerating adhesion between the exterior surface of the article and the coating. The inventive coating is applied to the surface of the fiber and the coating is exposed to a radiation source.