Thermoelectric generator (TEG) modules generally have a low conversion efficiency. Among the reasons for the lower conversion efficiency is thermoelectric (TE) material mismatch. Hence, it is imperative to carefully select the TE material and optimize the design before any mass-scale production of the modules. Here, with the help of Comsol-Multiphysics (5.3) software, TE materials were carefully selected and the design was optimized to achieve a higher conversion efficiency. An initial module simulation (32 couples) of unsegmented skutterudite Ba0.1Yb0.2Fe0.1Co3.9Sb12 (n-type) and Ce0.5Yb0.5Fe3.25Co0.75Sb12 (p-type) TE materials was carried out. At the temperature gradient T = 500 K, a maximum simulated conversion efficiency of 9.2% and a calculated efficiency of 10% were obtained. In optimization via segmentation, the selection of TE materials, considering compatibility factor (s) and ZT, was carefully done. On the cold side, Bi2Te3 (n-type) and Sb2Te3 (p-type) TE materials were added as part of the segmentation, and at the same temperature gradient, an open circuit voltage of 6.2 V matched a load output power of 45 W, and a maximum simulated conversion efficiency of 15.7% and a calculated efficiency of 17.2% were achieved. A significant increase in the output characteristics of the module shows that the segmentation is effective. The TEG shows promising output characteristics.