Recent research efforts have concentrated on the development of flexible and stretchable thermoelectric (TE) materials. However, significant challenges have emerged, including increased resistance and reduced electrical conductivity when subjected to strain. To address these issues, rigid semiconducting polymers and elastic insulating polymers have been incorporated and nanoconfinement effects have been exploited to enhance the charge mobility. Herein, a feasible approach is presented for fabricating stretchable TE materials by using a doped semiconducting polymer blend consisting of either poly(3-hexylthiophene) (P3HT) or poly(3,6-dithiophen-2-yl-2,5-di(2-decyltetradecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thienylenevinylene-2,5-yl) (PDVT-10) as the rigid polymer with styrene-ethylene-butylene-styrene (SEBS) as the elastic polymer. In particular, the blend composition is optimized to achieve a continuous network structure with SEBS, thereby improving the stretchability. The optimized polymer films exhibit well-ordered microstructural aggregates, indicative of good miscibility with FeCl3 and enhanced doping efficiency. Notably, a lower activation energy and higher charge-carrier concentration contribute to an improved electrical conductivity under high tensile strain, with a maximum output power of 1.39 nW at a ΔT of 22.4 K. These findings offer valuable insights and serve as guidelines for the development of stretchable p-n junction thermoelectric generators based on doped semiconducting polymer blends with potential applications in wearable electronics and energy harvesting.