An improved and efficient electrochemical N-acylation of chiral oxazolidin-2-ones has been achieved. The generation of the nitrogen anion is obtained under mild conditions and without addition of base or probase, by direct electrolysis of a solution of MeCN-TEAP containing the oxazolidinone. Acylation agents (acid chlorides or anhydrides) were added at the end of the electrolysis. N-Acylated products were isolated in high to excellent yields.