•Two novel bipolar host materials containing phenanthroimidazole and dimesitylborane are obtained.•High-performance green, yellow and red PhOLEDs based on two bipolar hosts have been demonstrated.•Very high and stable EL efficiencies are achieved.In this work, two novel bipolar host materials p-BPPI and m-BPPI containing phenanthroimidazole/dimesitylborane (Mes2B) with para- and meta-linkage have been designed, synthesized and characterized. The appending Mes2B moiety improves the thermal stability, electrochemical stability and carrier injection/transport ability of both target compounds. The test results of time-of-flight (TOF) and single-carrier devices show that both the new hosts possess bipolar charge-transporting characteristics. As a result, series of highly efficient green (66.3 cd A−1, 63.1 lm W−1, 18.2%), yellow (55.2 cd A−1, 66.6 lm W−1, 14.5%) and red (20.1 cd A−1, 20.4 lm W−1, 13.5%) PhOLEDs are achieved by using them as the universal host materials. The results indicate that bipolar host p-BPPI and m-BPPI have high potential in fabricating various color OLEDs for displays and lighting applications. Our study further enriches the selection of D and A group for phosphorescent host materials. The relationship between molecular structures and optoelectronic properties is discussed experimentally and theoretically.Two novel bipolar hosts containing phenanthroimidazole and dimesitylborane with para- and meta-linkage have been designed, synthesized and characterized. The appending Mes2B moiety improves the thermal stability, electrochemical stability and carrier injection/transport ability. Within these merit, we have fabricated highly efficient green (66.3 cd A−1, 63.1 lm W−1, 18.2%), yellow (55.2 cd A−1, 66.6 lm W−1, 14.5%) and red (20.1 cd A−1, 20.4 lm W−1, 13.5%) PhOLEDs by using these compounds as host materials. The results indicate that bipolar host p-BPPI and m-BPPI have high potential in fabricating various color OLEDs for displays and lighting applications.