Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble‐metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face‐centered‐cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand‐induced amorphization is realized by post‐synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application. A unique thiol molecule, namely bismuthiol I, is discovered, which can induce the amorphization of Pd nanomaterials by ligand exchange under ambient conditions. This method is applicable to different kinds of Pd nanomaterials without destroying their integrity. Notably, the obtained amorphous Pd nanoparticles show dramatically enhanced electrocatalytic activity and excellent durability toward the hydrogen evolution reaction.