Dibenzotetrathiafulvalene (DBTTF), dibenzotetraselenafulvalene, and tetrathiatetracene salts with tin(IV) hexachloride and alkyltin(IV) (alkyl = Me and Et) chloride anions were prepared by controlled current electrolyses of the donor molecules in solutions containing [NBu n 4] 2[SnCl 6] or SnR 2Cl 2 (R = Me or Et) and [Ph 3PhCH 2P]Cl. The obtained salts with [SnCl 6] 2−, [SnMe 2Cl 3] −, [SnEt 2Cl 3] − and [Sn 3Me 6Cl 8] 2− anions behave as typical semiconductors with electrical resistivities of 1 ×(10 1–10 5) Ω cm at 25 °C as measured for compacted pellets. Electronic properties of the salts are discussed on the basis of infrared, electronic reflectance, and X-ray photoelectron spectra together with X-ray analysis. A single crystal X-ray structure analysis of [DBTTF] 3− [Sn 3Me 6Cl 8]·PhCN showed that the salt contains a columnar structure consisting of a DBTTF +·/DBBTF +·/ DBTTF 0 unit and a novel trimerized tin(IV)anion [Sn 3Me 6Cl 8] 2−. The crystals are triclinic, space group P 1 , with cell dimensions a=12.931(2), b= 20.992(4), c=12.485(1) Å, α=90.07(1), β= 99.18(1), γ=79.41(1)° and Z=2. The least-squares refinement, based on 4183 independent reflections with | F o| > 3σ( F), converged at R=0.104.