Charge balance does matter for emission materials to obtain high-performance organic light-emitting diodes (OLEDs), and it is well-known that the electron-transporting ability is inferior to the hole-transporting for the majority of organic emitting materials, especially for blue-emitting compounds. Hence, systematically investigating the effect of the electron-withdrawing group on fluorophore is of vital importance. In this study, we designed and synthesized two deep-blue phenanthro[9,10-d]imidazole (PI) based materials named DPy-PPI and DmPy-PPI by using pyridine-containing groups as electron acceptor as well as adjusting the conjugation length. The photophysical, theoretical, thermal and electrochemical properties of the compounds were investigated systematically, and the relationship between the conjugation length of substituent groups on phenanthroimidazole and the EL performance was clarified. Both of them exhibited good thermal stability and high photoluminescence quantum yields. Non-doped devices based on DPy-PPI and DmPy-PPI as emitter achieved deep-blue emissions with the Commission Internationale de L'Eclairage (CIE) index of (0.14, 0.06) and (0.15, 0.08) and high external quantum efficiencies (EQEmax) of 4.24% and 3.74%, respectively. Meanwhile, using DPy-PPI and DmPy-PPI as the host materials, yellow-orange phosphorescent organic light-emitting diodes (PHOLEDs) were fabricated with EQEmax, CEmax and PEmax of 20.55%, 63.86 cd/A, 37.08 lm/W and 18.14%, 55.84 cd/A, 32.47 lm/W, respectively. Furthermore, the red PHOLEDs were also constructed using DPy-PPI and DmPy-PPI as the host with EQEmax, CEmax and PEmax of 14.53%, 17.04 cd/A, 18.51 lm/W and 16.62%, 23.58 cd/A, 21.16 lm/W, respectively. And we believe this work can provide some insight suggestions for scientific researchers to design deep-blue emitting materials.