The first synthesis of hexa(furan-2-yl)benzene derivatives is described. The RhCl3/i-Pr2NEt-catalyzed cyclotrimerization of di(furan-2-yl)acetylenes was an effective method for constructing hexa(furan-2-yl)benzene derivatives in good yields. Their 蟺-extended derivatives were also synthesized by Suzuki鈥揗iyaura coupling between hexakis(5-Bpinfuran-2-yl)benzene (Bpin = (pinacolato)boryl) and several aryl iodides.