Reported here for the first time are the oxidative couplings of alkynes and primary alcohols yielding conjugated enones. Although the BF(3)-catalyzed reaction of terminal alkynes with p-trifluoromethophenl(difluoro)-lambda(3)-bromane results in the fluoro-lambda(3)-bromanation of triple bonds to afford (E)-beta-fluorovinyl-lambda(3)-bromanes, reaction of an alkyne with the difluoro-lambda(3)-bromane in the presence of an alcohol and BF(3)-Et(2)O affords directly conjugated enones in good yields. The reaction proceeds in a highly stereo- and regioselective manner under metal-free conditions. Interestingly, no formation of enones was detected, when difluoro-lambda(3)-iodane p-CF(3)C(6)H(4)IF(2) Was used instead of the lambda(3)-bromane. A mechanism involving a lambda(3)-bromane-induced oxidation of an alcohol to an aldehyde, [2 + 2] cyclization with alkynes yielding 2H-oxetes, and finally the electrocyclic ring opening is discussed.