A new family of emissive donor–acceptor–donor (D–A–D) compounds has been developed by introducing two electron-donors into the 7,8-diaza[5]helicene core as a novel helical electron acceptor. The X-ray crystallographic analyses revealed the uniquely twisted and helical structures of these compounds in the solid states. Notably, some D-A-D compounds developed herein display distinct mechanochromic luminescence (MCL) in the solid state, and a D–A–D helicene shows circularly polarized luminescence (CPL) with a relatively high luminescence dissymmetry factor <i>g</i><sub>lum</sub> of ca. 10<sup>–3</sup>. Time-resolved spectroscopic analysis revealed the aspects of thermally activated delayed fluorescence characters of the helicenes. Furthermore, the emissive helicenes were applied as organic light-emitting diodes emitters.