Organic blue emitters capable of proceeding triplet–triplet annihilation (TTA) are of great importance for high‐efficiency blue organic light‐emitting diodes (OLEDs). Herein, two deep‐blue emitters PAPE and PAPF with two diphenylanthracene (DPA) moieties linked by fluorene and ether, respectively, together with a single DPA model emitter PAPES are synthesized and characterized. Theoretical calculations indicate that the TTA mechanism of these materials is energetically favorable, which is evidenced by platinum oct…