A series of host materials, 3,3′-linked carbazole-based molecules have been designed with phenyl and biphenyl spacers. Their optical and electrical properties can be fine-tuning by the spacers. Their HOMO energy levels depend on HOMO distributions within the range of −5.64 to −5.96eV. On the other hand, the three compounds have similar LUMO energy levels and triplet energies. Their thermal, photophysical, electrochemical and carrier mobilities properties were also systematically investigated. The relationship between the molecular structures and optoelectronic properties are discussed. A blue PHOLED device incorporating PBCz achieved a maximum external quantum efficiency, current efficiency, and power efficiency of 19.5%, 45.5cd/A and 43.8lm/W, respectively. Moreover a two-color, all-phosphor and single-emitting-layer WOLED hosted by PBCz was also achieved with a maximum external quantum efficiency, current efficiency and power efficiency of 24.6%, 76.3cd/A and 69.4lm/W respectively. Furthermore, we also utilized this versatile host for three-component RGB white PHOLEDs and show excellent performance. For example, combination of PBCz with FIrpic, Ir(ppy)2(acac) and Ir(MDQ)2(acac) in the active layer, the resulting WOLEDs showed three evenly separated peaks and gave a high efficiency of 49.2cd/A. The efficient PHOLEDs demonstrated that the versatile host PBCz has great potential for applications in the solid-state lighting.