Ethoxy vinyl esters (EVE: 2) were efficient reagents for promoting the asymmetric Pummerer reaction with high enantioselectivity and high yield in contrast to the generally used acid anhydrides. Increasing the electron-donating ability on the R function in EVE 2 tended to increase enantioselectivity. Consequently, effective asymmetric rearrangements were achieved using EVEs 2b, c bearing a methoxybenzoyloxy function.