1,3-Bisarylated-2,2′-biazulene 1 and 1,1′-bisarylated-2, 2′-biazulene 1′ were obtained by the SuzukiMiyaura 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%. © 2014 The Chemical Society of Japan.