Recently, solution-processable PhOLEDs have been attracting great interest for their low cost and high productivity relative to the vacuum-deposited devices. Similar to vacuum-deposited OLEDs, however, they usually suffer from serious efficiency roll-offs, especially in high brightness. Finding a feasible way and/or designing novel materials to increase efficiencies and reduce roll-offs simultaneously are highly desired. Herein, a new family of solution-processable cyclometalated iridium(III) phosphors with carbazole (Cz) and/or diphenylphosphoryl (Ph2PO) units functionalized main ligands has been designed. Owing to Cz and Ph2PO moieties possessing bulky steric effects, they can suppress the intermolecular strong packing and then decrease TTA effects and emission quenching. Meanwhile, the resulting OLEDs based on the designed phosphors exhibit considerable efficiencies and relatively small efficiency roll-offs. The device based on 4 containing both Cz and Ph2PO units realized a maximum current efficiency of 21.3 cd A(-1), accompanied by a small roll-off. By optimization of the configuration of OLEDs, the device performance can be further enhanced, demonstrating their potential for high-performance solution-processable PhOLEDs.