In summary, we have employed the planar achiral pyrene molecule and chiral naphthalenediimide-based triangular macrocycle R-NDI as donor and acceptor to synthesize organic cocrystals R-NDI-Py and S-NDI-Py through outer-surface π-π interactions. The supramolecular donor–acceptor co-assembly approach and the consiquent intermolecular CT interactions inherited and improved the circular polarized luminescence acti vity of R-NDI and S-NDI precursors, endowing R-NDI-Py and S-NDI-Py a rare deep-red and NIR emissiom at 675 nm with the maximum luminescent asymmetric g factor (glum) of +1.5×10^-2 and -1.0×10^-2. It also promoted the two-photon absorption pro perty of R-NDI-Py and S-NDI-Py, resulting in a deep-red and NIR emission centered on 680 nm, with a 184 nm red-shift compared with R-NDI and S-NDI precursors, and the two-photon absorption cross-section at 810 nm can be calculated up to 2.277 × 103 GM. The fluorescence, CPL and TPA experiments, crystal structure analysis and the theoretical calculation demonstrate the ad justability of the packing mode in the D–A self-assembly system, thereby offering an effective strategy for designing and synthesi zing multi-functional crystalline optical materials.