The necessity for new sources for greener and cleaner energy production to replace the existing ones has been increasingly growing in recent years. Of those new sources, the hydrogen evolution reaction has a large potential. In this work, for the first time, MoSe2 /Mo core-shell 3D-hierarchical nanostructures are created, which are derived from the Mo 3D-hierarchical nanostructures through a low-temperature plasma-assisted selenization process with controlled shapes grown by a glancing angle deposition system.