Embodiments of a thin-film heterostructure thermoelectric material and methods of fabrication thereof are disclosed. In general, the thermoelectric material is formed in a Group IIa and IV-VI materials system. The thermoelectric material includes an epitaxial heterostructure and exhibits high heat pumping and figure-of-merit performance in terms of Seebeck coefficient, electrical conductivity, and thermal conductivity over broad temperature ranges through appropriate engineering and judicious optimization of the epitaxial heterostructure.