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Cs2SnCl6 double perovskite has attracted wide attention as a promising optoelectronic material because of its better stability and lower toxicity than its lead counterparts. However, pure Cs2SnCl6 demonstrates quite poor optical properties, which usually calls for active element doping to realize efficient luminescence. Herein, a facile co-precipitation method was used to synthesize Te4+ and Er3+-co-doped Cs2SnCl6 microcrystals. The prepared microcrystals were polyhedral, with a size distribution around 1–3 μm. Highly efficient NIR emissions at 1540 nm and 1562 nm due to Er3+ were achieved in doped Cs2SnCl6 compounds for the first time. Moreover, the visible luminescence lifetimes of Te4+/Er3+-co-doped Cs2SnCl6 decreased with the increase in the Er3+ concentration due to the increasing energy transfer efficiency. The strong and multi-wavelength NIR luminescence of Te4+/Er3+-co-doped Cs2SnCl6 originates from the 4f→4f transition of Er3+, which was sensitized by the spin-orbital allowed 1S0→3P1 transition of Te4+ through a self-trapped exciton (STE) state. The findings suggest that ns2-metal and lanthanide ion co-doping is a promising method to extend the emission range of Cs2SnCl6 materials to the NIR region. [ABSTRACT FROM AUTHOR]