Significance The authors introduce the new P,S-ferrocenyl ligand 1 which, in combination with Pd(II), effectively promotes asymmetric allylic etherification of racemic allylic acetates. Using various alcohols under mild conditions, the products are obtained in good yields and excellent enantioselectivities. The pivotal finding reported here is the unprecedented observation of the effect of the electronic properties of alcohol substrates on the enantioselectivity of the reaction.