A series of bipolar host materials containing dibenzo[b,d]thiophene (DBT) or dibenzo[b,d]thiophene 5,5-dioxide core were successfully synthesized, and their physical, photophysical, and electrochemical properties were investigated. The three host materials showed well-localized electron distribution at the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states, as evidenced by theoretical calculations. Triplet energies of the new host materials are higher than 2.6eV, and the blend film with bis[2-(4,6-difluorophenyl)pyridinato-C-2,N](picolinato)iridium(III) (FIrpic) as a blue phosphorescent dopant showed highly efficient energy transfer between the host material and dopant.