The exploitation of cheap, stable, and efficient catalysts is highly significant and greatly valuable for hydrogenation reactions. A novel amorphous alloy hollow sphere with hierarchical pores was synthesized by using in situ generated H2 bubble as a soft template with the chemical reduction method, in which the co‐deposited calcium carbonate acts as a hard template for fabricating the porous structure. The optimized amorphous Co‐Fe‐1 %Zn‐B alloy shows excellent catalytic performance with 97.7 % of cinnamaldehyde (CAL) conversion and 100 % of cinnamyl alcohol (COL) selectivity, which is superior to the reported results catalyzed by Co‐based catalysts, and even to those of noble metal catalysts for the selective CAL hydrogenation to COL. The enhanced catalytic activity of the prepared amorphous alloy is ascribed to the large active surface area, hierarchically porous and hollow structure, and the synergistic effect of Fe and Zn in the materials. The synthesized amorphous alloy also shows good stability and can be recycled for more than five runs. A possible fabrication mechanism for the hollow amorphous alloy porous spheres was also proposed and discussed.