A cationic rhodium(I)/BINAP [2,2′-bis(diphenylphosphino)-1,1′-binaphthyl] complex is capable of catalyzing the [2 2 2] cycloaddition-aromatization of 1,6-diynes with cyclic enol ethers (2,3-dihydrofuran and dihydropyran) at room temperature to produce the corresponding aryl alkanol derivatives in good yields. In this process, a conjugated dihydrofuran showed a significantly higher reactivity than a nonconjugated one.