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In recent years, all-inorganic lead-halide perovskites have received extensive attention due to their many advantages, but their poor stability and high toxicity are two major problems. In this paper, a low toxicity and stable Cs₂SnCl₆ double perovskite crystals were prepared by aqueous phase precipitation method using SnCl₂ as precursor. By the XRD, ICP-AES, XPS, photoluminescence and absorption spectra, the fluorescence decay curve, the structure and photoluminescence characteristics of Ce³⁺-doped and undoped samples have been investigated in detail. The results show that the photoluminescence originates from defects. [<inline-formula> <math display="inline"> <semantics> <mrow> <mi>S</mi> <msubsup> <mi>n</mi> <mrow> <mi>S</mi> <msup> <mi>n</mi> <mrow> <mn>4</mn> <mo>+</mo> </mrow> </msup> </mrow> <mrow> <mn>2</mn> <mo>+</mo> </mrow> </msubsup> </mrow> </semantics> </math> </inline-formula>+V_Cl] defect complex in the crystal is formed by Sn²⁺ substituting Sn⁴⁺. The number of defects formed by Sn²⁺ in the crystal decreases with Ce³⁺ content increases. Within a certain number of defects, the crystal luminescence is enhanced with the number of [<inline-formula> <math display="inline"> <semantics> <mrow> <mi>S</mi> <msubsup> <mi>n</mi> <mrow> <mi>S</mi> <msup> <mi>n</mi> <mrow> <mn>4</mn> <mo>+</mo> </mrow> </msup> </mrow> <mrow> <mn>2</mn> <mo>+</mo> </mrow> </msubsup> </mrow> </semantics> </math> </inline-formula>+V_Cl] decreased. When Ce³⁺ is incorporated into the crystals, the defects of [<inline-formula> <math display="inline"> <semantics> <mrow> <mi>C</mi> <msup> <mi>e</mi> <mrow> <mn>3</mn> <mo>+</mo> </mrow> </msup> <msub> <mrow></mrow> <mrow> <mi>S</mi> <msup> <mi>n</mi> <mrow> <mn>4</mn> <mo>+</mo> </mrow> </msup> </mrow> </msub> </mrow> </semantics> </math> </inline-formula>+V_Cl] and [<inline-formula> <math display="inline"> <semantics> <mrow> <mi>S</mi> <msubsup> <mi>n</mi> <mrow> <mi>S</mi> <msup> <mi>n</mi> <mrow> <mn>4</mn> <mo>+</mo> </mrow> </msup> </mrow> <mrow> <mn>2</mn> <mo>+</mo> </mrow> </msubsup> </mrow> </semantics> </math> </inline-formula>+V_Cl] were formed and the crystal show the strongest emission. This provides a route to enhance the photoluminescence of Cs₂SnCl₆ double perovskite crystals.