We investigated the high-temperature thermoelectric properties of Ga:ZnO bulk compounds, synthesized using a simple and scalable solid-state process. The effects of a low gallium content (x <= 0.04 in Zn(1-x)GaxO(1+x/2))on the structural features and electrical/thermal properties are reviewed. Transmission electron microscopy analyses showed that 2D, nonperiodic defects had formed from a doping content as low as x = 0.01 Ga. The structural description of these nanoscale interfaces is, for the first time, carefully investigated in such low-Ga-content samples by HAADF-STEM analyses combined with structural modeling. It was found that the formation of head-to-head inversion twin (h-IT) boundaries and tail-to tail inversion boundaries (t-IB) in the bulk compounds is responsible for strong phonon scattering, while maintaining relatively good electrical conductivity and thereby enhancing the thermoelectric properties. The absolute value of the Seebeck coefficient decreases abruptly from 475 mu V/K for x = 0 down to 60 mu V/K for x = 0.005 at 350 K. At the same time, the electrical resistivity drops from 1 ohm cm for x = 0 to 1.7 x 10(-3) ohm cm for x = 0.005. For higher Ga additions (x > 0.01), the increase in electrical resistivity is likely linked to the formation of interface defects at a larger extent in the wurtzite structure. The thermal conductivity also drops sharply with the increase in the Ga content from similar to 33 W/m K for x = 0 to similar to 8 for x = 0.04 at 350 K. This study is progress toward the synthesis of other thermoelectric materials where nanoscale interfaces in bulk compounds provide tremendous opportunities for further enhancing both the phonon scattering and the overall figure of merit.