Pure and alkaline metal ion (Mg, Ca, Sr, Ba) doped Cerium oxide nanostructures were successfully synthesized by hydrothermal method. The structural, optical and compositional studies of the prepared nanoparticles were undertaken by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), Raman, X-ray photoelectron spectroscopy (XPS) and TEM analyses. The photocatalytic activity of prepared nanoparticles was analyzed using methylene blue dye. XRD pattern reveals that the prepared nanoparticles are polycrystalline nature and there is no any by-product related peaks were observed for the doped samples. The incorporation of dopants into the CeO2 nanoparticles was confirmed through PL, Raman and XPS spectra. The enhanced photocatalytic activity for the alkaline metal doped samples was observed compared to pure cerium oxide nanoparticles.