A unique morphology of SrTiO3 nanocubes precipitated on TiO2 nanowires is successfully synthesized in the form of a thin-film heterojunctioned TiO2/SrTiO3 photocatalyst using facile hydrothermal techniques. The formation mechanisms of the synthesized photocatalysts are meticulously studied and described. Growth of SrTiO3 single crystal nanocubes (≈50 nm in width) on anatase polycrystalline nanowires follows an in situ dissolution-precipitation pathway. This is consonant with the classic LaMer model. By analyzing the results of field emission scanning electron microscopy (FESEM), field emission transmission electron microscopy (FETEM), X-ray diffraction (XRD), energy dispersive X-ray (EDX) spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-vis spectrophotometry, a comprehensive structural and morphological characterization of the photocatalysts is established. FESEM images reveal that the anatase film comprises mainly of nanowires bristles while the tausonite film is primarily made up of nanocube aggregations. In comparison to the respective pristine semiconductor photocatalysts, the heterostructured photocatalyst demonstrates the highest efficiency in photocatalytic splitting of water to produce H2, 4.9 times that of TiO2 and 2.1 times that of SrTiO3. The enhanced photocatalytic efficiency is largely attributed to the efficient separation of photogenerated charges at heterojunctions of the two dissimilar semiconductors, as well as a negative redox potential shift in the Fermi level.