Organic–inorganic hybrid thermoelectric (TE) materials have attracted tremendous interest for harvesting waste heat energy. Due to their mechanical flexibility, inorganic‐organic hybrid TE materials are considered to be promising candidates for flexible energy harvesting devices. In this work, enhanced TE properties of Tellurium (Te) nanowires (NWs)‐ poly (3‐hexylthiophene‐2, 5‐diyl) (P3HT) hybrid materials are reported by improving the charge transport at interfacial layer mediated via controlled oxidation. A power factor of ≈9.8 µW (mK2)−1 is obtained at room temperature for oxidized P3HT‐TeNWs hybrid materials, which increases to ≈64.8 µW (mK2)−1 upon control of TeNWs oxidation. This value is sevenfold higher compared to P3HT‐TeNWs‐based hybrid materials reported in the literature. MD simulation reveals that oxidation‐free TeNWs demonstrate better templating for P3HT polymer compared to oxidized TeNWs. The Kang–Snyder model is used to study the charge transport in these hybrid materials. A large σE0 value is obtained which is related to better templating of P3HT on oxygen‐free TeNWs. This work provides evidence that oxidation control of TeNWs is critical for better interface‐driven charge transport, which enhances the thermoelectric properties of TeNWs‐P3HT hybrid materials. This work provides a new avenue to improve the thermoelectric properties of a new class of hybrid thermoelectric materials.