AbstractPure aromatic hydrocarbon materials (PHCs) represent a new generation of host materials for phosphorescent OLEDs (PhOLEDs), free of heteroatoms. They reduce the molecular complexity, can be easily synthesized and are an important direction towards robust devices. As heteroatoms can be involved in bonds dissociations in operating OLEDs through exciton induced degradation processes, developing novel PHCs appear particularly relevant for the future of this technology. In the present work, we report a series of extended PHCs constructed by the assembly of three spirobifluorene fragments. The resulting positional isomers present a high triplet energy level, a wide HOMO/LUMO difference and improved thermal and morphological properties compared to previously reported PHCs. These characteristics are beneficial for the next generation of host materials for PhOLEDs and provide relevant design guidelines. When used as a host in blue‐emitting PhOLEDs, which are still the weakest link of the field, a very high EQE of 24 % and low threshold voltage of 3.56 V were obtained with a low‐efficiency roll‐off. This high performance strengthens the position of PHC strategy as an efficient alternative for OLED technology and opens the way to a more simple electronic.