Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio-imaging, cell labeling, phototherapy, and photo-activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu15 (PPh3 )6 (PET)13 ]2+ , which exhibits bright emission in the near-infrared (NIR) region (≈720 nm) and crystallization-induced emission enhancement (CIEE) phenomenon. Single crystal X-ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu6 core and a, unique among metal clusters, "tri-blade fan"-like structure. An in-depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π-π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.