This study focuses on understanding the influence of low Sb doping on ZnO’s electrical, optical, and thermoelectrical properties, while also studying its structural and morphological parameters. For this, several ZnO films with varying Sb target current densities, in the range of 0–0.27 mA/cm2, were produced by DC magnetron sputtering in a confocal geometry. As a result, thin ZnO:Sb films with an average transparency in the visible region greater than 80% are obtained, revealing for optimized conditions an absolute Seebeck coefficient of 100 μV/K and a respective power factor of 1.1 mW∙m−1∙K−2 at 300 K, effectively modifying the electrical, optical, and thermoelectrical properties of the material and ensuring its suitability for heat harvesting applications. From atom probe tomography experiments, a larger Zn content is registered at triple junctions of the grain boundary, which matches the approximately 25 nm crystallite grain size derived from the X-ray diffraction analysis.