Sn-based perovskites are promising Pb-free photovoltaic materials with an ideal 1.3 eV bandgap. However, to date, Sn-based thin film perovskite solar cells have yielded relatively low power conversion efficiencies (PCEs). This is traced to their poor photophysical properties (i.e., short diffusion lengths (<30 nm) and two orders of magnitude higher defect densities) than Pb-based systems. Herein, it is revealed that melt-synthesized cesium tin iodide (CsSnI3) ingots containing high-quality large single crystal (SC) grains transcend these fundamental limitations. Through detailed optical spectroscopy, their inherently superior properties are uncovered, with bulk carrier lifetimes reaching 6.6 ns, doping concentrations of around 4.5 x 10(17) cm(-3), and minority-carrier diffusion lengths approaching 1 mu m, as compared to their polycrystalline counterparts having approximate to 54 ps, approximate to 9.2 x 10(18) cm(-3), and approximate to 16 nm, respectively. CsSnI3 SCs also exhibit very low surface recombination velocity of approximate to 2 x 10(3) cm s(-1), similar to Pb-based perovskites. Importantly, these key parameters are comparable to high-performance p-type photovoltaic materials (e.g., InP crystals). The findings predict a PCE of approximate to 23% for optimized CsSnI3 SCs solar cells, highlighting their great potential.