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Three new anthracene-based emitters, 4-(10-(9,9′-spirobi[fluoren]-2-yl)anthracen-9-yl)benzonitrile (SBF-AnCN), 4-(10-(9,9-diphenyl-9H-fluoren-2-yl)anthracen-9-yl)benzonitrile (DPF-AnCN) and 4-(10-(9,9-dimethyl-9H-fluoren-2-yl)anthracen-9-yl)benzonitrile (DMF-AnCN) are developed for deep blue organic light-emitting diodes (OLEDs). Their photophysical properties, thermal properties, molecular configurations and device performances have been systematically investigated. As verified by crystallographic study, these anthracene derivatives possess highly twisted configuration, leading to deep-blue light emission by restraining π-conjugation extension. Furthermore, the difference in the molecular packing manner may influence the photoluminescence quantum yields (PLQYs) in solid state and the proportion of singlet exciton harvested by triplet–triplet annihilation (TTA) process. A nondoped device fabricated …