The compound 13bH-tribenzo [a, cd, h] azulene [1] was prepared from 1-fluorenonecarboxylic acid [5] as the starting material via several steps. 8-Methyl-13bH-tribenzo [a, cd, h] azulene [3] was synthesized from other route, and the azulenylium perchlorate [4] was derived from [3] as black crystals. Furthermore, 9-ethoxy-13bH-tribenzo [a, cd, h]-5-azaazulene [22] and 8-ethoxy-13bH-tribenzo [a, cd, h]-6-azaazulene [31], novel azaazulenes incorporating fluorene moiety, were obtained from 1-ethoxycarbony 1-9-phenyl-9-fluorenol [7] and azaazulenes 9- (2-bromomethylphenyl)-9-fluorenol [3] as starting materials, respectively.