An easy route to α-(alkoxysilyl) acetic esters and their utilization is described. It involves a two-step sequence carried out in one pot: Rhodium catalyzed Si-H insertion of a carbenoid, generated by decomposition of N2CHCO2Et, followed by a nucleophilic attack onto the Si-Cl bond by an alcohol. Alkylation of the title esters, reduction of the ester function and finally oxidation of the C-Si bond provide a facile entry to 1, 2-diols.