A novel strategy is demonstrated for Lewis base-activated trifluoromethylsulfinylation of allylic alcohols. Controllable synthesis of structurally varied allylic trifluoromethanesulfones via sigmatropic rearrangements was performed, and trifluoromethanesulfinate esters were achieved. This metal-free, catalytic divergent transformation features good functional group tolerance and late-stage modification of bioactive molecules. Mechanistic studies suggested that Lewis bases interact with N-(trifluoromethylsulfinyl)phthalimide to generate an ion pair adduct followed by O-trifluoromethylsulfinylation with allylic alcohols.