The present study reports synthesis of phenathroimidazole derivatives structures following donor–acceptor relation for high performance deep-blue light emitting diodes. Herein, methyl substituted benzodioxin-6-amine phenanthroimidazoles Cz-SBDPI and TPA-SBDPI derivatives that provide the blue light were designed and synthesized. These Cz-SBDPI and TPA-SBDPI show higher glass transition (T_g) temperatures of 199 and 194 °C and demonstrate enhanced thermal properties. Apart from enhanced thermal stability these compounds also exhibit superior photophysical, electrochemical and electroluminescent properties. The non-doped carbazole based device display improved electroluminescent performances than those of TPA-based devices. The strong orbital-coupling due to decreased energy barrier between Cz-SBDPI transitions result in deep blue emission with CIE—0.15, 0.06. For non-doped Cz-SBDPI device; high L (brightness):12,984 cd/m²; η_c (current efficiency): 5.9 cd/A; η_p (power efficiency): 5.7 lm/W and η_ex (external quantum efficiency): 6.2% was observed. The results show that the D–A emitters can serve as simple but also as an effective approach to devise cheap electroluminescent materials that has high efficiency and can serve as OLED devices.