Herein, a deep blue emitter (PI‐TPB‐CN) with a synergistic effect of hybridized local and charge transfer excited state (HLCT) and aggregation‐induced emission (AIE) properties is successfully designed and synthesized to improve the performance of deep blue organic light‐emitting diodes (OLEDs). It is constructed using a 1,2,4,5‐tetraphenylbenzene (TPB) as an π‐conjugated AIE core being asymmetrically functionalized with a phenanthro[9,10‐d]imidazole (PI) as a weak donor (D) and a benzonitrile (CN) as an acceptor (A), thereby formulating D‐π‐A type fluorophore. Its HCLT and AIE properties verified by theoretical calculations, solvatochromic effects, and transient photoluminescence decay experiments, bring about a strong blue emission (452 nm) with a high photoluminescence quantum yield of 74% in the thin film. PI‐TPB‐CN is successfully employed as a blue emitter in OLEDs. Non‐doped OLED with the structure of ITO/HATCN (6 nm)/NPB (30 nm)/TCTA (10 nm)/PI‐TPB‐CN (30 nm)/TPBi (40 nm)/LiF (1 nm)/Al (100 nm) demonstrates excellent electroluminescence (EL) performance with blue emission (451 nm) and maximum external quantum efficiency (EQEmax) of 7.38%. The device with a thinner layer of PI‐TPB‐CN (20 nm) and TPBi (30 nm) exhibits a deeper blue emission (444 nm) with CIE coordinates of (0.16, 0.09), a low turn‐on voltage of 3.0 V, and EQEmax of 6.45%.