Thermoelectric (TE) materials can be used to convert the wasted heat from many different heat sources into electricity. In recent years, a series of binary and ternary pnictogen containing the small amounts of triels- or tetrels-doping, which include the A₁₁Pn_10-xT_x (A = Rb, Cs, Sr, Ba, Eu, Yb; Pn = Sb, Bi; and T = Si, Ge, Sn) systems has also been studied for its thermoelectric applications. In particular, according to the previous article about A₁₁Sb₁₀ (A = Ca, Yb) system reported by Prof. Kauzlarich and Prof. Snyder, if a solid-solution system of Ca_11-xYb_xSb₁₀ were successfully prepared, then the electronic property could be finely tuned between a metal and a semiconductor as in the Ca_1-xYb_xZn₂Sb₂ solid-solution. Therefore, we attempted to make this solid-solution system by introducing the mixed-cations of Ca2+ and Yb2+. In addition, we also allow the system to have the anionic doping as well. Thus, Ge and Sn atoms were introduced to replace some of Sn in the system. Therefore, in this research, we discuss our systematic experimental and theoretical investigations of the effect of multi doping using both of cationic and anionic elements on the quaternary tetrel compounds the Ca_11-xYb_xSb_10-yTt_y (Tt = Si, Ge; 1.29 ≤ x ≤ 9.65; y = 0.25, 0.48) System. These compounds have been synthesized by using either Sn metal-flux or arc-melting and characterized by both powder and single crystal X-ray diffractions. As a result, we expect to see the influence of cationic and anionic doping on the electronic properties as well as thermoelectric properties, the site-preference of cations and anions based on the QVAL values, and the rationale of some historically large ADP values on two particular atomic sites. In addition, we also discuss the results of SEM and EDS, and TGA analyses.