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 glycycloxypropyltrimethoxysilane (or other suitable silane) 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, optionally a second solvent, and at least one organic additive; casting the mixture by spin coating to form a porous silica based 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.