<p>Due to the conformational stability and straightforward synthesis, centrally chiral organic small molecules serve as ideal candidates for constructing multi-resonance thermally activated delayed fluorescence (CP-MR-TADF) materials, exhibiting circularly polarized luminescence (CPL) properties. However, the advancement of CP-MR-TADF materials exhibiting point chirality remains restricted primarily to carbon-based chiral compounds, and the sulfur-centered structures are very few. Herein, we report the synthesis of six pairs of sulfur-centered CP-MR-TADF enantiomers, achieved by covalently fusing <i>N</i>-substituted sulfoximine fragments featuring sulfur stereocenters to a widely used multiple resonance parent core. These novel CP-MR-TADF materials demonstrate blue-green or green emission peaking at 495–509 nm with narrow full widths at half maximum of less than 30 nm, small singlet-triplet energy gaps of down to 0.03 eV and high photoluminescence quantum yields of up to 92.8%. Furthermore, all enantiomers exhibit notable CPL properties with dissymmetry factors ranging from 0.6 × 10⁻³ to 5.4 × 10⁻³. This effort broadens the range of chiral CP-MR-TADF materials featuring sulfur-centered configurations and establishes a foundation for innovative molecular design strategies and potential applications in devices.</p>