Na8Al6Si6O24Cl2∶Mn and Na8Al6Si6O24Cl2∶Fe NIR phosphors were prepared by a solid-solid reaction at high temperature. Their crystal structures of fluorescent powder were investigated by using X-ray powder diffraction (XRD), and their NIR emission spectrum and excitation spectrum were measured at room temperature. The main emission peak of Mn5+ in the Na8Al6Si6O24Cl2∶Mn phosphor was observed at 1 200 nm in the NIR spectral region under 400 or 602 nm excitation, attributing to the 3A2—3T2 and 3A2—1E transitions of Mn5+ ions. The characteristic NIR luminescence of Mn5+ in sodalite is greatly enhanced by co-doping manganese and sulfur. A mechanism of the energy transfer between S－2 and Mn5+ was also proposed here. The main emission peak of Fe2+ ions in the Na8Al6Si6O24Cl2∶Fe phosphor was recorded at 1 000 nm in the NIR region under the excitation of 334 or 500 nm. This photoluminescence originated from the 3T1—5E transition of Fe2+. Such an emission in the NIR region suggests a potential application in improving solar spectrum to enhance the efficiency of silicon solar cells.