The crystal structure of [C6H5NH(CH3)(2)](2)Te2I10 consists of the N,N-dimethylanilinium cation and a hitherto unreported tellurium iodide anion Te2I102- [crystal data: C(8)H(12)NTel(5), monoclinic, P2(1)/c, a = 9.4787(2) Angstrom, b = 14.2874(3) Angstrom, c = 13.6869(3) Angstrom, beta = 95.1918(8)degrees, V = 1845.96(7) Angstrom(3), Z = 4]. The Te2I102- dianion is based on two edge-sharing Tel(6)(2-) octahedra, and interestingly, it builds up a three-dimensional Te(IV)-I open framework through extensive interconnecting (II)-I-... contacts. These (II)-I-... contacts (3.66-3.80 Angstrom) are significantly shorter than the corresponding sum of van der Waals radii (4.0 Angstrom) and may potentially promote charge carrier migration throughout the Te-I network. This material can also be drop-cast into thin films from a heated DMF solution.