Constant-current electrolysis, in an undivided cell, of Ph3P in the presence of a carboxylic acid in CH2Cl2 containing 2, 6-lutidinium perchlorate as the supporting electrolyte was shown to generate the corresponding acyloxyphosphonium ion, Ph3P+-OCOR, which was converted in situ to esters, amides, and β-lactams under mild conditions.