Pure and 1 at% gallium (Ga)-doped zinc oxide (ZnO) thin films have been prepared with a low-cost spin coating technique on quartz substrates and annealed at 500 °C in vacuum ∼10−3 mbar to create anion vacancies and generate charge carriers for photovoltaic application. Also, 0.5–1.5 at% extra zinc species were added in the precursor sol to investigate changes in film growth, morphology, optical absorption, electrical properties and photoluminescence. It is shown that 1 at% Ga–ZnO thin films with 0.5 at% extra zinc content after vacuum annealing for 60 min correspond to wurtzite-type hexagonal structure with (0001) preferred orientation, electrical resistivity of ∼9 × 10−3 Ω cm and optical transparency of ∼65–90% in the visible range. Evidence has been advanced for the presence of defect levels within bandgap such as zinc vacancy (VZn), zinc interstitial (Zni), oxygen vacancy (Vo) and oxygen interstitial (Oi). Further, variation in ZnO optical bandgap occurring with Ga doping and insertion of additional zinc species has been explained by invoking two competing phenomena, namely bandgap widening and renormalization, usually observed in semiconductors with increasing carrier concentration.