The novel tris(triphenylphosphine)rhodium chloride/boron trifuoride etherate [RhCl(PPh3)3/BF3⋅OEt2] co‐promoted the CC cross‐coupling of tertiary alcohols at the β‐position with aldehydes. This reaction provides an efficient synthesis of either structurally diverse 1,3‐diols or polysubstituted tetrahydropyrans by controlling the substrate structures, and it could be developed to a practical synthetic method for numerous natural products and medicinally important compounds.