Cu9.1Te4Cl3 is a new polymorphic compound in the class of coinage metal polytelluride halides. Copper is highly mobile, which results in multiple order-disorder phase transitions in a limited temperature interval from 240 to 370 K. Mainly as a consequence of thermal transport properties, the compound's thermoelectric figure of merit reaches values up to ZT = 0.15 in the temperature range between room temperature and 523 K. Its structure is closely related to that of Ag10Te4Br3, another coinage metal polytelluride halide, which represents the first p-n-p-switchable semiconductor approachable by a simple temperature change. The title compound outperforms Ag10Te4Br3 in terms of thermoelectric properties by 1 order of magnitude and therefore acts as a link between the class of p-n-p compounds and thermoelectric materials.