Recently, there has been growing interest in deep red (DR) and near-infrared (NIR) thermally activated delayed fluorescence (TADF) emitters due to their potential use in applications in bioimaging and night-vision displays. Herein, we designed and synthesized a series of red/NIR TADF emitters, DMAC, PXZ, and DPACz, that all contain the same electron-accepting PyBP (dibenzo [f, h] pyrido [2,3-b]quinoxaline) moiety. These compounds emit at 643 nm for DMACPyBP, 722 nm for DPACz PyBP, and 743 nm for PXZPyBP in toluene solution, while their thin films singlet-triplet energy gaps (ΔEST) are < 0.1 eV.DMACPyBP, with the weakest donor, has the highest ΦPL of 62.3%, the smallest ΔEST of 0.03 eV, and a fast reverse intersystem crossing rate constant (kRISC) of 0.5 × 105 s-1 in a 1 wt% doped film in CBP. In contrast, PXZPyBP, containing the strongest donor, has a lower ΦPL (21.2%), a relatively larger ΔEST (0.10 eV), and a slower kRISC (0.04 × 105 s-1). Thus, our work highlights the molecular design challenges involved in pushing emission into the NIR region while maintaing both TADF and high FPL in PyBP-based donor-acceptor emitters.