We synthesized four new emitting materials of triphenylamine derivatives, 1,3,5-tris (4'-(1 ''-phenyl-benzimidazol-2 ''-yl)phenyl)amine (TPBB), MeO-TPBB, Br-TPBB, and Bu-TPBB, and investigated the effects of substituent on their intermolecular interaction and luminescence characteristics. UV-vis absorption and photoluminescence (PL) spectra of the TPPB derivatives measured in dilute solution were almost the same but, in solid state, the PL spectra exhibited large differences depending on the substituent. Especially, the PL spectra of Br-TPPB redshifted remarkably in solid state. We also prepared electroluminescent devices with the multilayer structure of [ITO/NPB (50 nm)/EML (30 nm)/TPBI (20 nm)/Alq3 (10 nm)/LiF (1 nm)/Al] using one of the TPBB derivatives as an emitting layer. The TPBB derivatives showed much different electroluminescence (EL) characteristics depending on the nature of the substituent. This suggests that each substituent present different degree of intermolecular electronic interaction in the TPBB derivatives.