1,3-Bisarylated-2,2'-biazulene 1 and 1,1'-bisarylated-2,2'-biazulene 1' were obtained by the Suzuki-Miyaura crosscoupling reaction of 1,1',3,3'-tetrahalo-2,2'-biazulene 2 with 4-tert-butylphenylboronic acid (3b). The other two halogen atoms were reductively removed by hydrogenation under the same reaction conditions. The major regioisomer 1 was obtained with a selectivity of up to 94% (15:1) and a combined yield of 1 and 1' of up to 77%.