AbstractWOCl4reacts at 200°C with tellurium in a sealed, evacuated ampoule with the formation of Te6(WOCl4)2. The structure consists of six‐membered tellurium rings in a boat conformation with significant transannular interactions and of pyramidal WOCl4units which are linked by linear asymmetric O...;WO bridges to polymeric (WOCl4)n, chains. The observed paramagnetism is consistent with the ionic formulation Te2+6[(WOCl−4)2]n. In the reaction of WCl6, I2and Te in a 2:1:6 ratio Te6I2(WCl6)2is formed at 150°C. The crystal structure consists of Te6I2+2cations and of slightly distorted octahedral WCl−6anions. The Te6I2+2ions are isostructural with Se6I2+2and consist of a six‐membered ring of Te atoms in the chair conformation with two I atoms bound in the 1,