The development of low-cost electrode materials with enhanced activity and favorable durability for hydrogen evolution reactions (HERs) is a great challenge. MoSsub.2 is an effective electrocatalyst with a unique layered structure. In addition, aluminosilica shells can not only provide more hydroxyl groups but also improve the durability of the catalyst as a protective shell. Herein, we have designed a hard-template route to synthesize porous yolk–shell MoSsub.2 @void@Aluminosilica microspheres in a NaAlOsub.2 solution. The alkaline solution can directly etch silica (SiOsub.2 ) hard templates on the surface of MoSsub.2 microspheres and form a porous aluminosilica outer shell. The electrocatalytic results confirm that the MoSsub.2 @void@Aluminosilica microspheres exhibit higher electrocatalytic activity for HERs with lower overpotential (104 mV at the current density of −10 mA cmsup.−2 ) and greater stability than MoSsub.2 microspheres. The superior electrocatalytic activity of MoSsub.2 @void@Aluminosilica microspheres is attributed to the unique structure of the yolk@void@shell geometric construction, the protection of the aluminosilica shell, and the greater number of active sites offered by their nanosheet subunits. The design of a unique structure and new protection strategy may set up a new method for preparing other excellent HER electrocatalytic materials.