C–N Axial Chirality in Donor–Acceptor Luminophores: A Design Strategy for Circularly Polarized Luminescence‐Active Systems

C–N axial chirality remains largely unexplored in luminescent molecules due to its inherently low configurational stability, despite its potential for chiroptical applications. Herein, we report the design and synthesis of donor–acceptor (D–A)‐type molecules incorporating benzo[ b ]phenoxazine (BPO) as an asymmetric electron donor and dicyanobenzene as an electron acceptor. These molecules were efficiently synthesized via nucleophilic aromatic substitution, enabling straightforward access to C–N axially chiral architectures. It was demonstrated that steric substitution at both ortho ‐positions of the BPO unit effectively increases the rotational barrier around the C─N bond, allowing optical resolution. These compounds exhibited dual emission arising from locally excited (LE) states of the BPO unit and charge‐transfer (CT) states, along with long‐lived emission in the solid matrix attributable to triplet‐state‐mediated processes. Notably, these compounds exhibit enhanced circularly polarized luminescence (CPL) at low temperature, attributable to suppression of conformational fluctuations around the C–N axis. These results demonstrate an effective molecular design strategy for CPL emitters based on C–N axial chirality.