Amorphous metal-oxide semiconductors can be readily prepared by a solution process at low temperatures, and their energy band structures and carrier concentrations can be controlled based on the oxide composition or the addition of dopants in the design of thermoelectric (TE) materials. However, research on the correlation between the charge transport and TE performance of amorphous metal-oxide semiconductors is still in its infancy. Herein, we present the energy-dependent TE performance characteristics of Li-doped ZnO thin films with different doping levels and charge carrier concentrations. Thin films were prepared by the solution process, and the Li doping level was controlled by the Li precursor concentration added to a Zn precursor solution. Subsequently, a field-effect-modulated Seebeck coefficient measurement device was built to study the energy-dependent TE performance. Notably, the higher ratio of interstitial Li (Liinter) and oxygen vacancies (Ova) in the Li-ZnO device indicates an improved n-type TE performance. To investigate more thoroughly the charge transport phenomena, the localized density of states (DOS) was derived from the temperature-dependent transfer curve; the higher ratio of interstitial Li (Liinter) and oxygen vacancy (Ova) induces a reduction in the localized DOS and lowers the degree of disorder in their DOS. The determined energy-dependent TE characteristics can be used as guidance for the design of efficient TE devices with amorphous metal-oxide semiconductors.