The synthesis of surface-active structures is important for creating many applications. The structural formation of SnO2 thin films in the range from 1.4 to 1.53 pH is studied in this work. This process occurs on the surface of the sample in the range of 1.4 to 1.49 and in the volume in the range of 1.51 to 1.53. SnO2 is formed after annealing at 400 ∘C, according to XRD. Doping NH4OH to solution stimulates particle coagulation and gel formation. All of these have an impact on the transparency of samples investigated by spectrophotometric methods. By increasing the pH, the resistance raises at room temperature. The Eg calculation along the fundamental absorption edge shows that it is greater than 3.6 eV’ for SnO2 films. According to the Burstein−Moss effect, a change of the bandgap is related to the increased concentration of the free charge carriers. Elemental analysis has shown that chlorine ions are considered to be additional sources of charge carriers. The value pH = 1.49 is critical since there is a drastic change in the structure of the samples, the decrease in transparency is replaced by its increase, and the energy of activation of impurity levels is changed.