The novel ambipolar hosts of o-CbzBz and o-DiCbzBz contain carbazole and benzimidazole through an ortho-connection. The orthogonal conformations cause the triplet state to be confined at the carbazole units to secure efficient energy transfer. The phosphorescent organic light-emitting diodes (PhOLEDs) show a high current efficiency, power efficiency, and low efficiency roll-off. o-DiCbzBz can be used as a host for sky-blue, green, and orange-red PhOLEDs, giving 57.5, 78.4, and 60.3 cd/A, respectively.