Organic blue emitters have been get more and more attention by scientists and industries in the field of organic light-emitting diodes (OLEDs). The design of efficient blue emitters, especially deep-blue ones, is still a challenge because of their intrinsic wide band-gaps and unbalanced carrier mobilities. Herein, two donor‒π‒acceptor (D‒π‒A) type molecules with phenanthro[9,10-d]imidazole (PI) as A and pyridinyl as π-bridge were designed and synthesized by fine-turning the D moieties, namely mPTPA and mP3PCZ, respectively. Theoretical calculation and single-crystal analysis showed that there exist intramolecular hydrogen bond (IHB) interactions inducing small torsion angles between pyridinyl and adjacent phenyls. The rigid 9-phenyl-9H-carbazole (PCZ) and IHB interactions makes mP3PCZ exhibiting planar configuration along the long-axis of the molecule, which could increase the orbital overlap and oscillator strength (f_os). The solvatochromic effect manifested that both two emitters have hybridized local and charge-transfer (HLCT) characteristics, and the excited state of mP3PCZ exhibited LE-dominated HLCT state which is beneficial for high photoluminescence efficiency. Ultimately, the non-doped devices based on mPTPA and mP3PCZ achieved maximum luminance larger than 12000 cd m⁻². Furthermore, the doped device based on mP3PCZ exhibited maximum external quantum efficiency of 5.14% with low efficiency roll-off, and with the corresponding deep-blue Commission international de l’éclairage (CIE) coordinate of (0.166, 0.085).