Micro-/nano-structured SrSnO3/x wt.-% TiO2 composites (x = 10, 20, and 30) were designed using a mixed method, a typical hydrothermal and impregnation method, to enhance hydrogen production from MeOH/H2O photo-splitting. All the materials obtained exhibited a perovskite structure. Scanning electron microscopy revealed pure SrSnO3 to have a rod-like morphology with a square base, 0.7-1.5 μm in size, and a height of approximately 2.0-3.0 μm. Moreover, phenomena were observed in the rods similar to that of typical perovskite with a layered structure. TiO2 nanoparticles, < 100 nm in size, were observed in the SrSnO3/TiO2 materials and the number of particles increased with increasing Ti concentration. The SrSnO3 material absorbed shorter band edges of less than 300 nm compared to that of pure TiO2, and the UV-visible absorption spectra were shifted to high wavelengths with the TiO2, loading. Hydrogen evolution from MeOH/H2O (1:1) photosplitting over the micro-/nano-structured SrSnO/TiO2 composite was enhanced compared to that over pure SrSnO3. In particular, 0.033 mmol of H2 gas was collected after 10 h under an 18 W-lamp with 365 nm radiation when 0.5 g of a SrSnO3/TiO2 20 wt.-% composite was used. Based on cyclic voltammetry and ultraviolet-visible spectroscopy, it was expected that the high photo activity resulted from the decrease in electron-hole recombination on the micro-/nano-structured SrSnO3/TiO2 composite.