Hydrogen production from the photocatalytic reforming of glycerol aqueous solution was performed on the CuO@TiO2, NiO@TiO2, NiO@CuO, and CuO@NiO core-shell nanostructured catalysts under simulated solar light irradiation. These catalysts were prepared by the combination of a modified sol-gel and a precipitation-deposition method using hydroxypropyl cellulose as structural linker and they were characterized by powder X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (UV–Vis DRS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen physisorption isotherms techniques. The catalysts containing TiO2 as a shell and CuO as core showed much higher activity compared with those formulated with NiO@CuO, CuO@NiO, and bared CuO or NiO nanoparticles. The highest rate of hydrogen production obtained with the CuO@TiO2 catalyst was as high as 153.8 μmol·g−1h-1, which was 29.0, 24.8, 11.2 and 3.2 times greater than that obtained on CuO@NiO, NiO@CuO, TiO2 P25, and NiO@TiO2 catalyst, respectively. For the high active CuO@TiO2 catalyst, after activation of TiO2 with solar light irradiation, the conduction band electrons can be transferred to CuO core through the heterojunction in the core-shell interfaces which led to CuO gradually reduced to Cu2O, favoring the reduction of proton to release hydrogen.