Three D-A-D-configured molecules DTPBT, DTPNT, and DTPNBT with high quantum yield of orange red (628 nm), red (659 nm), and deep-red/NIR (710 nm) fluorescence, respectively, were developed as emitting dopants in an exciplex-forming cohost (TCTA:3P-T2T) for high-efficiency fluorescence-based organic light-emitting diodes (OLEDs). The obtained physical properties together with theoretical calculations analyzed from these new molecules establish a clear structure-property relationship, in which the feature of central acceptor 2,1,3-benzothiadiazole (BT), naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole (NT), and 2,1,3-naphthothiadiazole (NBT) plays the crucial role for governing the physical characteristics. The optimized device configured as ITO/HAT-CN/TAPC/TCTA/TCTA:3P-T2T:5% emitter/3P-T2T/LiF/Al gave a record-high efficiency of orange red (591 nm, 15%), red (647 nm, 10%), and deep-red/NIR (689 nm, 9%) electroluminescent devices. The effective harvest of triplet excitons with an exciplex-forming system in conjunction with efficient energy transfer between the exciplex and the dopant is beneficial for such high device efficiencies. More importantly, the stable exciplex-forming cohost and fast radiative decay rate of DTPNT render this particular device exhibiting high device stability as indicated by the low efficiency roll-off under high current densities (EQE (external quantum efficiency) values of 8.1% at 1000 cd m and 6.8% at 10,000 cd m). These results reveal the potential of employing an exciplex-forming system as cohost for fluorescent dopants to furnish high-efficiency OLEDs with an emission wavelength extending to the red or even the NIR range.