N-Heterocyclic carbenes (NHCs) with a variety of oxidants promote the Mitsunobu-type coupling reactions of alcohols with phenols, carboxylic acids, and phthalimide. Experiments using a chiral alcohol indicate that these reactions proceed via S_N1 or S_N2 pathways depending on the polarity of the used solvents. The NHCs are consumed as reducing reagents to form their oxides as readily separable byproducts.