Thermally activated delayed fluorescence (TADF) materials with both high photoluminescence quantum yield (PLQY) and fast reverse intersystem crossing (RISC) are strongly desired to realize efficient and stable organic light-emitting diodes (OLEDs). Control of excited-state dynamics via molecular design plays a central role in optimizing the PLQY and RISC rate of TADF materials but remains challenging. Here, 3 TADF emitters possessing similar molecular structures, similar high PLQYs (89.5% to 96.3%), and approximate energy levels of the lowest excited singlet states (S1), but significantly different spin-flipping RISC rates (0.03 × 106s−1vs. 2.26 × 106s−1) and exciton lifetime (297.1 to 332.8 μs vs. 6.0 μs) were systematically synthesized to deeply investigate the feasibility of spin-flip between charge-transfer excited states (3CT–1CT) transition. Experimental and theoretical studies reveal that the small singlet–triplet energy gap together with low RISC reorganization energy between the3CT and1CT states could provide an efficient RISC through fast spin-flip3CT–1CT transition, without the participation of an intermediate locally excited state, which has previously been recognized as being necessary for realizing fast RISC. Finally, the OLED based on the champion TADF emitter achieves a maximum external quantum efficiency of 27.1%, a tiny efficiency roll-off of 4.1% at 1,000 cd/m2, and a high luminance of 28,150 cd/m2, which are markedly superior to those of the OLEDs employing the other 2 TADF emitters.