Cs7Nd11(SeO3)12Cl16, the complex selenite chloride of cesium and neodymium, was synthesized in the NdOCl-SeO2-CsCl system. The compound has been characterized using single-crystal X-ray diffraction, electron diffraction, transmission electron microscopy, luminescence spectroscopy, and second-harmonic-generation techniques. Cs7Nd11(SeO3)12Cl 16 crystallizes in an orthorhombic unit cell with a = 15.911(1) Å, b = 15.951(1) Å, and c = 25.860(1) Å and a noncentrosymmetric space group Pna21 (No. 33). The crystal structure of Cs7Nd11(SeO3)12Cl16 can be represented as a stacking of Nd11(SeO3) 12 lamellas and CsCl-like layers. Because of the layered nature of the Cs7Nd11(SeO3)12Cl16 structure, it features numerous planar defects originating from occasionally missing the CsCl-like layer and violating the perfect stacking of the Nd 11(SeO3)12 lamellas. Cs7Nd 11(SeO3)12Cl16 represents the first example of a noncentrosymmetric structure among alkaline-metal lanthanide selenite halides. Cs7Nd11(SeO3) 12Cl16 demonstrates luminescence emission in the near-IR region with reduced efficiency due to a high concentration of Nd3+ ions causing nonradiative cross-relaxation.