Thermoelectricity is a strong scientific and technological interest due to its wide application ranging from clean energy producing to photon sensing devices. Recent developments in theoretical studies on the thermoelectric (TE) effects as well as the newly discovered thermoelectric materials provide new opportunities for several applications. Though the scale of production is limited, thermo-electric technology provides an alternative to traditional methods of power generation, heating and cooling systems. TE technologies can be used in power generation, heating and cooling applications. They potentially offer significant energy savings through waste heat recovery and augmented cooling. This article critically discusses the current progress in chalcogenide TE materials and the advantages and limitations associated with the TE technologies. The need for new materials discoveries from the point of view of achieving higher figure-of-merit combined with thermal stabilities in intermediate- and high- temperature Peltier and Seebeck effects applications is also emphasized. Besides, this article aims to evaluate the main features of recently characterized multicomponent chalcogenide ionic compounds with high thermal stabilities as potential TE materials to harvest electric power from high-temperature heat flux via thermoelectricity.