A selection of mixed conducting silver chalcogenide halides of the general formula Ag₅<i>Q</i>₂<i>X</i> with <i>Q</i>=sulfur, selenium and tellurium and <i>X</i>=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag₅Te₂Cl showed a defined <i>d</i>¹⁰-<i>d</i>¹⁰ interaction in the disordered cation substructure at elevated temperatures where Ag₅Te₂Cl is present in its high temperature <i>α</i>-phase. A significant drop of the thermal diffusivity has been observed during the <i>β−α</i> phase transition reducing the values from 0.12 close to 0.08 mm² s⁻¹. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values. Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag₅<i>Q</i>₂<i>X</i> were determined around the silver -order/disorder <i>β−α</i> phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the <i>β−α</i> phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m⁻¹ K⁻¹ at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag₅<i>Q</i>₂<i>X</i> phases.Read less <