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The present invention relates to Ca and Yb mixed quaternary zintl compounds and to a manufacturing method thereof. In the present invention, a new zintl compound was synthesized by replacing Yb, which is an expensive rare earth metal, with an inexpensive Ca. Since the replacement of the zintl compound increases the degree of confusion of the structural complexity and the atomic mass so that the zintl compound is a new thermoelectric material having a similar thermal conductivity to the conventional thermoelectric material even though the Yb content has decreased. Therefore, the Ca and Yb mixed quaternary zintl compounds of the present invention are thermoelectric materials which are economical and have excellent thermoelectric efficiency, and are expected to be used as a thermoelectric material composition of a thermoelectric generator to further activate an environmentally friendly energy recovery field using waste heat.COPYRIGHT KIPO 2018