The combination of methanesulfonic acid and potassium bifluoride is reported for the deoxyfluorination of tertiary alcohols. Under metal-free conditions that use readily available, cheap, and easy-to-handle reagents, a range of tertiary alcohols could be converted into the corresponding fluorides in excellent yields (average yields of 85% for 23 examples). Mechanistic investigation showed that the reaction proceeds at 0 °C, in part, through an elimination/hydrofluorination pathway, but no residual alkenes are observed. The application of these conditions for the fluorination of ether and ester is also demonstrated.