An improved and efficient electrochemical N-acylation of chiral oxazolidin-2-ones has been achieved. Thegeneration of the nitrogen anion is obtained under mildconditions and without addition of base or probase, by directelectrolysis of a solution of MeCN−TEAP containing theoxazolidinone. Acylation agents (acid chlorides or anhydrides) were added at the end of the electrolysis. N-Acylatedproducts were isolated in high to excellent yields.