The advancement of desirable circularly polarized luminescence (CPL) emitters is predominantly constrained by the effective regulation of magnetic and electric transition vectors, particularly within the deep-blue spectral domain. Herein, we present four pairs of novel chiral emitters with systematically varied molecular rigidity, symmetry, and chiral centers to elucidate the intrinsic coupling of key molecular parameters influencing their chiroptical properties. Notably, the incorporation of appropriate intramolecular 3D-interlocking within a natural binaphthyl chirality skeleton offers an effective approach to achieving both significantly narrowed full width at half maximum (FWHM, as low as 18 nm) and substantially enhanced chiroptical activity (luminous dissymmetry factor,