Zinc sol deposited via dip coating on Fluorine-doped Tin Oxide (FTO) coated glasses were annealed at 450 °C in normal ambient to form ZnO layers. The effect of annealing durations, i.e. 30, 60, 90, and 120 min on their surface morphology, crystallinity, optical, electrical and Dye-Sensitized Solar Cells (DSSCs) performance were studied. The XRD analyses indicated the formation of wurtzite ZnO after 60 min of annealing. It is noted that the ZnO layers annealed at 60-120 min showed good crystal quality attributed to its sharp, narrow and strong diffraction peaks. Generally, ZnO layers with uniform thickness have been deposited on the FTO coated glasses. The thickness of ZnO layers decreased from 0.88, 0.78, 0.76, and 0.73 mm when the annealing duration increased from 30 to 120 min due to removal of hydrocarbons from the zinc sol. The O at. % increased with annealing duration, indicating that more oxygen reacted with zinc to form ZnO. The ZnO thin film annealed at 60 min had relatively low sheet resistance (9.6 W) with optical bandgap of 3.04 eV. This suggests that ZnO layers annealed at 60 min have the largest amount of oxygen vacancies that contributed electrons for charges transportation in the layers. Besides, the Room Temperature Photoluminescence (RTPL) analyses showed that the ZnO thin film annealed for 60 min showed IUV/IVis ratio = 0.89, suggesting better crystal quality compared to shorter annealing duration.