The invention relates to a spherical core-shell type LaNiAl-SiO2 compound hydrogen storage material applicable to hydrogen separation and a preparation method thereof, and belongs to the field of hydrogen storage materials. LaNiAl alloy has a composition general formula of LaNi5-xAlx, wherein x is more than or equal to zero and less than or equal to 2; the spherical material has an outer diameter of 4-6mm, an intermediate main ingredient of LaNiAl alloy, a porous SiO2 appearance and a thickness of 1-2mm. The preparation process of a material comprises the steps of melting and powdering alloy; stirring, mixing and granulating the alloy powder with silica sol; coating with gaseous SiO2; and performing aging and hydrothermal removing treatment. The preparation method of the compound hydrogen storage material has high automatic degree, uniform appearance and size and small airflow resistance, has maximal filling capacity in a reactor, cannot be ground or further pulverized, and cannot block a filter or cause self-compaction, so that toxicity of CO, O2, NH3, H2S and other impure gases for LaNiAl alloy can be greatly reduced, and the service life is greatly prolonged. The spherical core-shell type LaNiAl-SiO2 compound hydrogen storage material can be used in a hydrogen separating process.