Lithium (Li)-assisted indium oxide (In2O3) thin films with ordered structures were prepared on solution-processed zirconium oxide (ZrO2) gate dielectrics by spin-casting and thermally annealing hydrated indium nitrate solutions with different Li nitrate loadings. It was found that the Li-assisted In precursor films on ZrO2 dielectrics could form crystalline structures even at processing temperatures (T) below 200 °C. Different In oxidation states were observed in the Li-doped films, and the development of such states was significantly affected by both temperature and the mol% of Li cations, [Li+]/([In3+] + [Li+]), in the precursor solutions. Upon annealing the Li-assisted precursor films below 200 °C, metastable indium hydroxide and/or indium oxyhydroxide phases were formed. These phases were subsequently transformed into crystalline In2O3 nanostructures after thermal dehydration and oxidation. Finally, an In2O3 film doped with 13.5 mol% Li+ and annealed at 250 °C for 1 h exhibited the highest electron mobility of 60 cm2 V−1 s−1 and an on/off current ratio above 108 when utilized in a thin film transistor.