Phenanthroimidazole (PI) has great proficiency to design efficient near UV deep blue emitting materials due to its bipolarity behavior. The tuning of N1 and C1 centers of the PI further reveals the improvement of the optical and electronical properties. Thorough investigation is also executed to explore the influence of the alkyl chain on the optical and electroluminescence (EL) properties of these emissive materials. The incorporation of the alkyl chain in the materials can tune the optical properties, leading to better solid state emission and enhancement of the photoluminescence quantum yield (PLQY) of thin film (∼74%) as compared to solution (∼65%). The EL spectra were also exhibited between 395 and 420 nm (in the near-UV spectral region). Furthermore, for boosting of the device efficiency and color purity, the OLED device is fabricated by doping CBP as host matrix. Selectively, CBP is used as a host because of the similar energy level (HOMO and LUMO) of the synthesized emitters which assist efficient charge trapping. Predominantly, the emitters in OLED device blended with 0.5 wt % concentration achieved brilliant device efficiency and luminance properties. Among all the synthesized fluorophores, PIPP (0.5 wt %) doped OLED device showed 4.4% maximum external quantum efficiency (EQEmax), 1202 cd/m2 highest luminance, 2.2 lm/W power efficiency (PE), 2.7 cd/A current efficiency (CE) with Commission International de L'Eclairage (CIE) coordinates x = 0.17, y = 0.10 (nearer the NTSC standard value). © 2023 American Chemical Society.