Recently, it was reported that the novel thermoelectric Zintl compound in the Yb_2-xEu_xCdSb₂ system adopting the Yb₂CdSb₂-type structure showed decent ZT values. However, the cationic mixing of Ca²⁺ and Yb²⁺ has not been reported yet. In addition, considering previously known two Zintl phases the Ca₂CdSb₂ and the Yb₂CdSb₂ compounds, the Ca²⁺/Yb²⁺ cation mixing can provide some interesting perspectives for the Zintl phase TE materials. Thus, a series of Ca_2-xYb_xCdSb₂ compounds were synthesized by the Pb-flux reactions, and its crystal structure was characterized by both of the powder and single crystal X-ray diffractions. According to SXRD refinement, it was clear that the compounds having the relatively larger Ca content adopted the Ca₂CdSb₂–type, while the compounds having the relatively larger Yb content adopted the Yb₂CdSb₂-type structure. The Ca₂CdSb₂–type structure adopts the orthorhombic space group Pnma, and the Yb₂CdSb₂-type compounds crystalize in the Cmc2₁. In addition, both structures contain five independent atomic sites. Tight-binding linear muffin-tin orbital calculations were also performed to understand chemical bonding and the overall electronic structure. In this process, density of states and crystal orbital Hamilton population were thoroughly interrogated. As a result, the Ca₂CdSb₂–type compound showed the semiconductor behavior with narrow band gap, while the Yb₂CdSb₂-type displayed the poor metallic behavior with a pseudogap. Thermoelectric property measurements for these compounds are underway.