Novel walnut-like SnO2 spheres have been synthesized using a one-step hydrothermal reaction with SnCl2·2H2O and KOH as raw materials. The morphology, microstructure, and optical properties of the products were characterized by X-ray powder diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and ultraviolet-visible (UV-Vis) absorption spectroscopy. The detailed studies revealed that these synthesized spheres are highly monodisperse and have a uniform size of approximately 250 nm. Photocatalytic activity of the prepared SnO2 spheres was evaluated by the degradation of methylene orange. The synthesized SnO2 spheres exhibited excellent photocatalytic degradation. In addition, a possible formation mechanism of the walnut-like nanostructures was proposed based on reaction time-dependent experiments.