Organic light-emitting diodes (OLEDs), which have been recently utilized in some flat-panel display screens such as mobile phones and televisions, show many merits, including light weight, high flexibility, energy preservation, and so forth, and are considered the next-generation displays and solid-state lightings. Blue-emitting materials that can be applied in nondoped OLEDs with little efficiency roll-offs at high brightness are of great importance. Here, a highly efficient, blue-emitting material, 9-phenyl-10-(4-(pyren-1-yl)phenyl)-9H-pyreno [4,5-d]imidazole (PyPI-Py), is achieved using pyrene [4,5-d]imidazole and pyrene as the weak electron donor and electron acceptor, respectively. The nondoped blue OLED exhibits excellent performance with a maximum brightness of 75,687 cd m −2 , a maximum current efficiency of 13.38 cd A −1 , and a maximum external quantum efficiency (η ext ) of 8.52%. Moreover, the η ext is maintained at 8.35% and 8.05% at a brightness of 10,000 and 50,000 cd m −2 , respectively, displaying extremely small efficiency roll-offs of 2.0% and 5.5%.The device characteristics are among the highest values for nondoped blue OLEDs and correspond to the best performance obtained for nondoped pyrene-based blue OLEDs. The superior performance is attributed to the proper donor-acceptor design strategy which results in a quasi-equivalent hybrid local and charge-transfer excited state with the maximum generation of an 82% fraction of singlet excitons.