AbstractAlthough bowl‐shaped N‐pyrrolic polycyclic aromatic hydrocarbons (PAHs) can achieve excellent electron‐donating ability, their application for optoelectronics is hampered by typically low photoluminescence quantum yields (PLQYs). To address this issue, we report the synthesis and characterization of a series of curved and fully conjugated nitrogen‐doped PAHs. Through structural modifications to the electron‐accepting moiety, we are able to switch the mechanism of luminescence between thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP), and to tune the overall PLQY in the range from 9 % to 86 %. As a proof of concept, we constructed solid‐state organic light‐emitting diode (OLED) devices, which has not been explored to date in the context of concave N‐doped systems being TADF/RTP emitters. The best‐performing dye, possessing a peripheral trifluoromethyl group adjacent to the phenazine acceptor, exhibits yellow to orange emission with a maximum external quantum efficiency (EQE) of 12 %, which is the highest EQE in a curved D‐A embedded N‐PAH to date.