A series of novel blue phosphorescent host materials, namely, CTP-1, CTP-2 and CTP-3 have been designed and synthesized through the Suzuki–Miyaura cross-coupling reaction between N-phenylcarbazole and biphenyl. Their thermal, photophysical and electrochemical properties were systematically investigated. These novel hosts show excellent thermal stability and high glass transition temperatures (Tg) ranging from 113 to 127 °C. The triplet energies of these three materials are significantly higher than that of (4,4′-bis(N-carbazolyl)-2,2′-biphenyl) (CBP, 2.56 eV) and that of the most popular blue phosphorescent material iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C2′] picolinate (FIrpic, 2.65 eV). These three novel materials have superior thermal and electronic properties for blue and white phosphorescent OLEDs. Blue emitting devices with an Ir-complex FIrpic as the phosphorescent dopant have been fabricated and show high efficiency with low roll-off. In particular, 40.4 cd A−1 at 100 cd m−2 and 38.2 cd A−1 at 1000 cd m−2 were achieved when CTP-1 was used as the host material. On the basis of this work, an all-phosphor white device with a current efficiency of 64.5 cd A−1 at 100 cd m−2 and 61.9 cd A−1 at 1000 cd m−2 has also been fabricated.