Process for the production of alkoxysilanes of the formula HSi(OR)3, where R is an alkyl group containing 1 to 6 carbon atoms, and/or alkyl orthosilicates of the formula Si(OR)4, where R is an alkyl group containing 1 to 6 carbon atoms. In a preferred embodiment, the process comprises reacting silicon metal with an alcohol in a suitable solvent in the presence of a cupric bis(diorganophosphate) catalyst. A polymeric form of ethyl orthosilicate, a by-product of the reaction, is the preferred solvent. The production of triethoxysilane and tetraethyl orthosilicate is preferred, with triethoxysilane being particularly preferred.