Vacancy-ordered double perovskites Cs2SnX6 (X = Cl, Br, I) have emerged as promising lead-free and ambient-stable materials for photovoltaic and optoelectronic applications. To advance these promising materials, it is crucial to determine the correlations between physical properties and their local structure and dynamics. Solid-state NMR spectroscopy of multiple NMR-active nuclei (133Cs, 119Sn and 35Cl) in these cesium tin(IV) halides has been used to decode the structure, which plays a key role in the materials’ optical properties. The 119Sn NMR chemical shifts span approximately 4000 ppm and the 119Sn spin-lattice relaxation times span three orders of magnitude when the halogen goes from chlorine to iodine in these diamagnetic compounds. Moreover, ultrawideline 35Cl NMR spectroscopy for Cs2SnCl6 indicates an axially symmetric chlorine electric field gradient tensor with a large quadrupolar coupling constant of ca. 32 MHz, suggesting a chlorine that is directly attached to Sn(IV) ions. Variable temperature 119Sn spin lattice relaxation time measurements uncover the presence of hidden dynamics of octahedral SnI6 units in Cs2SnI6 with a low activation energy barrier of 12.45 kJ/mol (0.129 eV). We further show that complete mixed-halide solid solutions of Cs2SnClxBr6−x and Cs2SnBrxI6−x (0 ≤ x ≤ 6) form at any halogen compositional ratio. 119Sn and 133Cs NMR spectroscopy resolve the unique local SnClnBr6−nand SnBrnI6−n (n = 0−6) octahedral and CsBrmI12−m (m = 0−12) cuboctahedral environments in the mixed-halide samples. The experimentally observed 119Sn NMR results are consistent with magnetic shielding parameters obtained by density functional theory computations to verify random halogen distribution in mixed-halide analogues. Finally, we demonstrate the difference in the local structures and optical absorption properties of Cs2SnI6 samples prepared by solvent-assisted and solvent-free synthesis routes.