Selective C‐O bond cleavage is of high interest for modern organic synthesis. A strategy for selective allylic C‐O bond cleavage using ethyl salicylate as a directing leaving group has been developed. The reaction is initiated by the chelation of the ortho‐ester phenolic group with iron catalyst. The pi‐allyl iron intermediate is generated and reacts with Grignard reagents to give the allylic substitution products. The excellent selectivity of C‐O bond cleavage is achieved in multiple allylic C‐O bond‐containing substrates with the aid of the salicylate‐directed strategy.