Reaction of dibenzofuran(Ⅱ) with sec-butyl lithium (s-BuLi)/tetramethyl ethylene diamine (TMEDA) /acetaldehyde(CH3CHO) gave 1,1'-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-ol)(Ⅲa) which was then oxidized by pyridinium chlorochromate (PCC) to yield 1,1'-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-one)(Ⅳa). Subsequent reduction of IV-A by borane-dimethyl sulfide (BH3-Me2S) in the presence of a catalytic amount of  (S)-2-methyl-CBS-oxazo borane{(S)-MeCBS} followed by recrystallization gave optically pure (1R,1'R)-1,1'- (dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-ol) (Ⅰ). The optimal reaction conditions are as follows: the molar ratio of Ⅱ: s-BuLi: TMEDA: CH3CHO is 1: 3: 3.3: 2.2, the molar ratio of Ⅲa: PCC is 1: 4, the molar ratio of Ⅳa: (S)-MeCBS: BH3-Me2S is 1: 0.6: 3, and the overall yield of the three-step reaction is 32%. An intramolecular hydrogen bond of compound (Ⅰ) affects further diversifications of its hydroxyl group to some extent. The racemic 1,1'-(dibenzo[b,d]furan-4,6-diyl)bis(ethan-1-amine) (Ⅶ) was obtained starting from Ⅲa via a successive process of chlorination with thionyl chloride, azidination with sodium azide and Pd/C-catalyzed hydrogenation. However, the resolution of Ⅶ by commonly used chiral carboxylic acids to obtain optically pure 1,1'-(dibenzo[b,d]furan-4,6 -diyl)bis(ethan-1-amine)(Ⅷ) was not successful.