With a view to attain balanced charge flux for higher device performance of PhOLEDs, we have used carbazole/triphenyl amine as hole transporting moiety and cyano along with benzimidazole as electron transporting core in 3-Cbz-ImdCN, 4-Cbz-ImdCN and TPA-ImdCN. Their thermal, photophysical and electrochemical properties have been evaluated to shed light on structure-property-performance relationship. Good performances have been exhibited by these bipolar host materials in green PhOLEDs with maximum external quantum efficiencies were observed in the range of 5.3–11.5% using Ir(ppy)3 emitter. Further, 3-Cbz-ImdCN hosted orange and red PhOLEDs with the Ir(MDQ)2acac and Ir(piq)2acac emitters revealed the external quantum efficiencies of 5.1% and 6.3%, respectively. In all the devices pure emission was observed from dopants only which clearly implies that the devices possess effective energy transfer from the host to the guest. Display omitted •Bipolar host materials comprising carbazole/triphenyl amine and cyanobenzimidazole were synthesized.•Structure-property-performance relationship studied using different linking topology.•HOMO energy levels are located on donors while LUMO populated on acceptors.•The green PhOLEDs showed maximum external quantum efficiencies in the range of 5.3–11.5%.•3-Cbz-ImdCN hosted red PhOLED revealed the external quantum efficiency of 6.3%.