ABSTRACT A highly efficient iridium‐catalyzed ring‐opening reactions of heterobicyclic alkenes with fluoroalkyl alcohols has been developed. The reaction utilizes readily available fluoroalkyl alcohols as fluoroalkoxylation reagents and exhibits a wide substrate scope, affording the fluoroalkoxylated products with trans ‐1,2‐disubstituted dihydronaphthalene framework in good to excellent yields. Mechanistic insights, supported by computational studies, have been proposed to elucidate the reaction pathway.