We have developed a novel electrolytic system for anodic acyloxylation based on the acid-base reactions between acetic acid or trifluoroacetic acid and solid-supported bases. On the basis of the electrolytic system, anodic acyloxylation of organic compounds, which even have considerably high oxidation potentials, was successfully carried out to provide the corresponding acyloxylated products in moderate to excellent yields. Furthermore, it was found that silica gel supported bases are not only chemically stable under acidic conditions but also electrochemically stable and thus reusable for many times. (C) 2009 Elsevier Ltd. All rights reserved.