Tremendous efforts have been devoted to develop efficient deep blue organic light-emitting diodes (OLEDs) materials with CIEy < 0.10 (Commission International de L’Eclairage (CIE)) and match the National Television System Committee (NTSC) standard blue CIE (x, y) coordinates of (0.14, 0.08) for display applications. However, deep blue fluorescent materials with an external quantum efficiency (EQE) over 5% are still rare. Herein, we report a phenanthroimidazole–sulfone hybrid donor–acceptor (D–A) molecule with efficient deep blue emission. D–A structure molecular design has been proven to be an effective strategy to obtain high electroluminescence (EL) efficiency. In general, charge transfer (CT) exciton formed between donor and acceptor is a weak coulomb bonded hole–electron pair and is favorable for the spin flip that can turn triplet excitons into singlet ones. However, the photoluminescence quantum yield (PLQY) of CT exciton is usually very low. On the other hand, a locally excited (LE) state normally possesses high PLQY owing to the almost overlapped orbital distributions. Hence, a highly mixed or hybrid local and charge transfer (HLCT) excited state would be ideal to simultaneously achieve both a large fraction of singlet formation and a high PLQY and eventually achieve high EL efficiency. On the basis of such concept, phenanthroimidazole is chosen as a weak donor and sulfone as a moderate acceptor to construct a D–A type molecule named as PMSO. The PMSO exhibits HLCT excited state properties. The doped device shows deep blue electroluminescence with an emission peak of 445 nm and CIE (0.152, 0.077). The maximum external quantum efficiency (EQE) is 6.8% with small efficiency roll-off. The device performance is among the best results of deep blue OLEDs reported so far.