A novel near ultraviolet (NUV) emitter with a meta-linked donor–acceptor (D–A) structure between triphenylamine (TPA) and phenanthroimidazole (PPI), mTPA–PPI, was designed and synthesized. This molecular design is expected to resolve the conflict between the non-red-shifted emission and the introduction of a charge-transfer (CT) state in the D–A system, aiming at NUV organic light-emitting diodes (OLEDs) with high-efficiency and colour-purity. Theoretical calculations and photophysical experiments were implemented to verify the unique excited state properties of mTPA–PPI. The mTPA–PPI device exhibited excellent NUV electroluminescence (EL) performance with an emission peak at 404 nm, a full width at half maximum (FWHM) of only 47 nm corresponding to a CIE coordinate of (0.161, 0.049), and a maximum external quantum efficiency (EQE) of 3.33%, which is among the best results for NUV OLEDs. This work not only demonstrates the promising potential of mTPA–PPI in NUV OLEDs, but also provides a valuable strategy for the rational design of NUV materials by using the meta-linked D–A architecture.