A series of bipolar transport host materials: 2,5‐bis(2‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (o‐CzOXD) (1), 2,5‐bis(4‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (p‐CzOXD) (2), 2,5‐bis(3‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (m‐CzOXD) (3) and 2‐(2‐(9H‐carbazol‐9‐yl)phenyl)‐5‐(4‐(9H‐carbazol‐9‐yl)phenyl)‐1,3,4‐oxadiazole (op‐CzOXD) (4) are synthesized through simple aromatic nucleophilic substitution reactions. The incorporation of the oxadiazole moiety greatly improves their morphological stability, with Td and Tg in the range of 428–464 °C and 97–133 °C, respectively. The ortho and meta positions of the 2,5‐diphenyl‐1,3,4‐oxadiazole linked hybrids (1 and 3) show less intramolecular charge transfer and a higher triplet energy compared to the para‐position linked analogue (2). The four compounds exhibit similar LUMO levels (2.55–2.59 eV) to other oxadiazole derivatives, whereas the HOMO levels vary in a range from 5.55 eV to 5.69 eV, depending on the linkage modes. DFT‐calculation results indicate that 1, 3, and 4 have almost complete separation of their HOMO and LUMO levels at the hole‐ and electron‐transporting moieties, while 2 exhibits only partial separation of the HOMO and LUMO levels possibly due to intramolecular charge transfer. Phosphorescent organic light‐emitting devices fabricated using 1–4 as hosts and a green emitter, Ir(ppy)3 or (ppy)2Ir(acac), as the guest exhibit good to excellent performance. Devices hosted by o‐CzOXD (1) achieve maximum current efficiencies (ηc) as high as 77.9 cd A−1 for Ir(ppy)3 and 64.2 cd A−1 for (ppy)2Ir(acac). The excellent device performance may be attributed to the well‐matched energy levels between the host and hole‐transport layers, the high triplet energy of the host and the complete spatial separation of HOMO and LUMO energy levels.