The remarkable electrocatalytic properties of silver for organic halide reduction have been applied to obtain quantitative direct dehalogenation of mono and polyphenols in acetonitrile and in water/acetonitrile 1: 1 mixed solvent. Structure effects on the reaction pathways observed by electrolysis monitoring are discussed with the support of systematic cyclovoltammetric experiments on silver, mercury, and glassy carbon. The process, environmentally friendly as based on a nontoxic electrocatalytic material, also appears highly competitive on account of its mildness of operating conditions, selectivity, and current efficiency.© 2001 The Electrochemical Society. All rights reserved.