Enhancing the optical anisotropy of compounds has attracted significant interest in the optical field. Sn-centered crystals, containing stereochemically active lone pairs, are widely regarded as promising birefringent materials. In this study, we successfully synthesized two novel Sn-centered mixed halide birefringent crystals, NaSn2F4Br and Na2Sn2F5I. These crystals, composed of Sn-centered mixed halide polyhedra, exhibit more than a 2-fold increase in birefringence from NaSn2F4Br to Na2Sn2F5I. Among all known Sn-centered halides, the Na2Sn2F5I crystal demonstrates the highest birefringence (Δn = 0.408@546 nm). Theoretical calculations indicate that the exceptional optical properties of Na2Sn2F5I arise from the large polarization anisotropy induced by the Sn-I bond within the Sn-centered polyhedra. These findings provide valuable insights for the development of high-quality birefringent crystal materials in Sn-centered mixed halide systems.