This study demonstrates a proficient and eco-friendly synthesis of SnO2 nanostructures using a hydrothermal method, without the requirement of extra surfactants. The synthesis was systematically performed by adjusting the molar ratio of stannic chloride to sodium hydroxide and varying the pH settings. It was noted that the pH value rises according to the concentration of sodium hydroxide. A comprehensive analysis was performed to characterize the resulting nanostructures, which involved studying their structural features, chemical composition, morphology, and optical properties. An X-ray diffraction (XRD) analysis showed that increasing the pH values resulted in a noticeable improvement in the crystalline structure and a decrease in the density of surface defects. The SnO2 nanostructures, synthesized using different pH settings, were subsequently assessed for their photocatalytic performance in the degradation of methylene blue (MB) dye under simulated solar irradiation. Surprisingly, the nanostructure produced at higher pH levels showed outstanding results, as 97% of the dye was broken down in just 70 minutes when exposed to simulated solar radiation. The analysis uncovered a maximum rate constant (k) value of 0.04 min−1, determined using pseudo first-order rate kinetics. In order to better understand the photodegradation process, scavenger experiments were performed to identify the active species involved. These investigations provided valuable insights into the complex mechanisms that drive the observed photocatalytic activity. This study not only enhances the progress of SnO2 nanostructures but also highlights their potential as strong and environmentally friendly materials for effective photocatalytic applications.