A star‐shaped molecule with a central electron‐deficient triazine ring connected to three electron‐rich N‐annulated perylene tetraesters was synthesized. Its application as an emissive layer in the fabrication of a sole and host–guest solution processable OLED, exhibiting bright green emission with good electroluminescence efficiency is demonstrated. A star‐shaped donor–acceptor molecule containing a central triazine and three perylene tetraester moieties exhibits bright green electroluminescence. This study also provides insights into the molecular design of highly emissive materials as well as the ability to control the singlet and triplet energy differences and may pave the way towards new materials with thermally activated delayed fluorescence (TADF).