Sn19.3Cu4.7As22I8, a new clathrate-I compound with a cationic host framework containing transition metals, has been synthesized, and its crystal structure has been determined. It crystallizes in the cubic space group Pm (3) over barn with a unit cell parameter a = 11.1736(3) angstrom and Z = 1 (R = 0.031 for 329 independent reflections and 22 variables). Tin, copper, and arsenic form the cationic clathrate framework hosting the guest iodine anions in cages of two different shapes. Sn(19.3)Cu(4.7)AS(22)I(8) does not contain vacancies in the framework but reveals three partially occupied positions of the metal atoms, leading to the formation of Sn-Sn and Sn-Cu bonds that differ in length. The Sn-119 Mossbauer spectrum confirms the local environment of tin atoms. The hyperfine constants obtained from the Mossbauer spectra for different cationic tin clathrates are discussed. Electron diffraction and electron microscopy reveal that the splitting affects the short-range ordering but does not lead to a superstructure. Though containing a transition metal, Sn19.3Cu4.7As22I8 is diamagnetic, and its composition corresponds to the Zintl formalism.