The future of organic light-emitting devices (OLEDs) is drifting from electrofluorescence toward electrophosphorescence due to the feasibility of realizing 100% internal quantum efficiency. There is limited availability of transition metals (TMs) such as Ir, Os, and Pt, which are used for color-tunable phosphorescent emitters, and the use of the host-guest strategy is necessary for suppressing the detrimental triplet–triplet annihilation inherently imparted by the TM-centered emitters. The inevitable demands of organic host materials provide organic chemists with tremendous opportunities to contribute their expertise to this technology. With suitable molecular design and judicious selection of chemical structures featured with different electronic nature, the incorporation of hole-transporting (HT) and electron-transporting (ET) moieties combines the advantages of both functional units into bipolar host materials, which perform balanced injection/transportation/recombination of charge carriers and consequentially lead the OLEDs to have higher performancesand low roll-off efficiencies. This review highlights recently developed bipolar host materials with the focus on molecular design strategies and the structure–property–performance relationships of various classes of bipolar host materials, which are classified into several categories according to the structural features of their constituents (HT/ET blocks and spacers).