Tellurium tetrachloride and allylphenyl sulfide react to form (1-thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-trichloride. The crystal and molecular structure were determined by single-crystal X-ray techniques. The crystals belong to the monoclinic system, space group P2(1)/c (No. 14) with a = 6.020(3) Angstrom, b = 11.46(1) Angstrom, c = 20.156(2) Angstrom, beta = 97.53(2)degrees, V = 1379(1) Angstrom(3), and Z = 4. The structure was refined to the final R value of 0.036. The coordination around Te-IV is distorted psi octahedral with three Cl atoms in the equatorial positions. The axial Te(1)-C(1) bond opposite to the lone pair of electrons at the Te-IV atom completes the coordination polyhedron. The intramolecular Te-S distance is 2.903(3) Angstrom. Symmetric and asymmetric deformation modes were established to describe the plasticity of the Cl-Te-Cl fragments extracted from the Cambridge Structural Database. The hypervalency of Te-IV manifests itself as plasticity in the equatorial plane of the coordination sphere. The NBO calculations show that all of the equatorial Te-CI bonds are highly polarized and the electrons reside mainly on the Cl atoms.