The first highly enantioselective [3 + 2] formal cycloaddition of 1-styrylnaphthols (or phenol) with quinones catalyzed by a chiral phosphoric acid has been reported. A class of trans-2,3-diarylbenzofurans were prepared efficiently (up to 99% yield, >20:1 dr, 99% ee). This organocatalytic procedure allows lowering of the catalyst loading to 0.5 mol % without considerable loss in reactivity and enantioselectivity.