A new series of starburst triarylamine fluorophores SBCHO, DBCHO, CZCHO, CZCN, and SBCN, that incorporate diphenylamine or carbazole as the electron donor and dicyanovinyl or aldehyde as the electron acceptor, has been prepared and their photophysical properties are investigated. In sharp contrast to most red-emitting dopants, which show serious aggregation-caused quench phenomena, the new starburst triphenylamine derivatives reported here show unique enhanced emission in the solid state or upon aggregation. Organic light emitting diodes using these compounds as non-doped host emitters and hole transporters have been fabricated. The highest external quantum yield reaches 2.09 % for CZCHO. SBCHO was investigated as a chlorine gas fluorescence (FL) solid-film sensor for the first time. The high-intensity emission was ‘turned off' immediately after being blown by Cl2 gas.