Highly efficient deep-red organic light-emitting devices (OLEDs) are indispensable for developing high performance red-green-blue (RGB) displays and white OLEDs (WOLEDs). However, the shortage of deep-red emitters with high photoluminescence quantum yields (PLQYs) and balanced charge injection/transport abilities have severely restricted the performance of deep-red OLEDs. Herein, we design and synthesize four efficient emitters by combining the isoquinoline group with the thianthrene 5,5,10,10-tetraoxide group. Benefited from the introduction of the thianthrene 5,5,10,10-tetraoxide group, these Ir(III) complex show improved electron injection/transport abilities. By enhancing the contribution of the triplet metal-to-ligand charge transfer (3MLCT) in emissions, the asymmetric configuration endows the related deep-red Ir(III) complexes with high PLQYs of 0.45-0.50 in solutions. More importantly, PLQYs of these Ir(III) complexes in doped host films increase up to 0.91, which is much higher than PLQYs reported for conventional deep-red Ir(III) complexes with impressive electroluminescent performance. As a result, solution-processed OLEDs based on these Ir(III) complexes exhibit deep-red emissions with Commission Internationale de L'Eclairage (CIEx,y) coordinates very close to the NTSC (National Television System Committee)-recommended standard red CIE coordinates of (0.67, 0.33). Furthermore, a deep-red OLED using the asymmetric Ir(III) complex SOIrOPh as the emitter shows outstanding performance with a peak external quantum efficiency (EQE) of 25.8%, which is the highest EQE reported for solution-processed deep-red OLEDs. This work sheds light on the great potential of utilizing the thianthrene 5,5,10,10-tetraoxide group to develop phosphorescent emitters for highly efficient OLEDs.