AbstractDespite being studied for nearly 50 years, smallest chemically stable moieties in the metallic glass (MG) could not be found experimentally. Herein, we demonstrate a novel experimental approach based on electrochemical etching of amorphous alloys in inert solvent (acetonitrile) in the presence of a high voltage (1 kV) followed by detection of the ions using electrolytic spray ionization mass spectrometry (ESI MS). The experiment shows stable signals corresponding to Pd, PdSi and PdSi₂ ions, which emerges due to the electrochemical etching of the Pd₈₀Si₂₀ metallic glass electrode. These fragments are observed from the controlled dissolution of the Pd₈₀Si₂₀ melt-spun ribbon (MSR) electrode. Annealed electrode releases different fragments in the same experimental condition. These specific species are expected to be the smallest and most stable chemical units from the metallic glass which survived the chemical dissolution and complexation (with acetonitrile) process. Theoretically, these units can be produced from the cluster based models for the MG. Similar treatment on Pd₄₀Ni₄₀P₂₀ MSR resulted several complex peaks consisting of Pd, Ni and P in various combinations suggesting this can be adopted for any metal-metalloid glass.