We have developed hypervalent iodine(III) induced oxidative olefination of primary and secondary benzylamines using 2C-Wittig reagents, which provides easy access to α,β-unsaturated esters. Mild reaction conditions, good to excellent yields with high (E) selectivity, and a broad substrate scope are the key features of this reaction. We have successfully carried out the gram-scale synthesis of α,β-unsaturated esters.