The reductive etherification of aldehydes can be performed by the reaction with dialkylmethylsilanes in the presence of new iron(II) piano-stool catalysts of general formula Cp*Fe(Co)(2)Ar (Cp* = eta(5)-C5Me5; Ar = Ph, 4-C6H4OCH3, 4-C6H4CH3, Fc). This transformation is promoted by UV light and affords a simple route for the preparation of unsymmetrical alkyl ethers. (C) 2012 Elsevier Ltd. All rights reserved.