The development of efficient blue emitter–host combinations is one of the biggest challenges in organic light-emitting diode (OLED) research. Host materials play a crucial role when it comes to enhancing the efficiency, improving the lifetime and decreasing the efficiency roll-off of the device. The need for new hosts is of prime importance, especially for blue phosphorescence and thermally activated delayed fluorescence (TADF) emitters, due to their high exciton energies. The hosts are less investigated than the emitters and require further progress. This work provides a new molecular strategy that combines an acridine derivative (donor) and pyrimidine moieties (acceptors) to obtain three novel host materials. This approach demonstrates that via careful selection of donor and acceptor units, it is possible to manage the properties of the host materials, obtaining at the same time superior thermal and morphological properties and high triplet energies up to 3.07 eV. The decrease of the conjugation in the acceptor unit was found to play a crucial role in increasing the triplet energy. The most promising host 1MPA was used to fabricate blue TADF OLEDs. Using a sky-blue emitter, we achieved electroluminescence at 491 nm and a maximum external quantum efficiency (EQE) of 13.6%, combined with a low efficiency roll-off, even beyond the practical brightness of 1000 cd m−1. The host 1MPA was also combined with a deep blue emitter to deliver a blue OLED with color coordinates of x = 0.16 and y = 0.18.