Spiro[fluorene-9,9′-xanthene] (SFX) bipolar hosts bearing one, two and three quinolyl substituents, namely SFX-bPy, SFX-DbPy and SFX-TbPy, were designed and synthesized for phosphorescent organic light emitting diodes (PhOLEDs). The successive substitution of quinoline at 2′, 2 and 7′ positions of SFX results in reduced LUMO energy levels while leaving the HOMO energy levels nearly intact. The impact of quinoline substitution in these SFX-based hosts on PhOLED performance was investigated in detail through green and red model devices. For the green emitting devices, the device based on SFX-bPy host showed better performance (23.6 cd A-1, 23.4 lm W-1, 6.3%) due to high triplet energy level (T1) and balanced carriers-transporting ability. In contrast, for the red PhOLED devices, the device hosted by SFX-DbPy displayed higher performance (15.8 cd A-1, 16.0 lm W-1, 9.1%), attributable to the well matched T1 and separated frontier molecular orbitals. This work thus sheds light on the rational design of SFX-based bipolar hosts for more efficient PhOLEDs.