A method of making an anti-reflection coating using a sol-gel process, for use in a photovoltaic device or the like. The method may include the following steps in certain example embodiments: forming a polymeric component of silica by mixing silane(s) with one or more of a first solvent, a catalyst, and water; forming a silica sol gel by mixing the polymeric component with a colloidal silica, and optionally a second solvent; forming a combined sol by mixing siloxane(s) with the silica sol; casting the mixture by spin coating or the like to form a silica and siloxane containing layer on a substrate; and curing and/or heat treating the layer. This layer may make up all or only part of an anti-reflection coating which may be used in a photovoltaic device or the like.