Electrochemical oxidation of optically active N-acylated alpha-amino acids gave N,O-acetals with enantioselectivity of up to 83% ee. The nature of the protecting groups, reaction conditions, and the materials for anode were found to affect the enantioselectivity. The mechanistic aspect of this electrochemical oxidation was also investigated. (C) 2003 Elsevier Ltd. All rights reserved.