The cyclic trimer of dibenzofuran linked at the 4,6-positions, named [3] cyclo-4,6-dibenzofuranylene, was synthesized by Ni(0)-mediated reductive coupling of 4,6-dibromodibenzofuran. DFT calculation indicated that the flake-shaped C-2 symmetric structure is the most stable conformer and the propeller-shaped D-3 symmetric structure is the minor conformer with a higher energy (+19.1 kcal mol(-1)). The calculated inversion energy of the C2 conformer through a C-s symmetric transition state was +4.1 kcal mol (1) 1, showing rapid fluctuation, which is consistent with the observation of only one set of (HNMR)-H-1 signals of dibenzofuran of [3] cyclo-4,6-dibenzofuranylene.