Due to the great limitation of glass forming ability, precisely controlling the chemical compositions of metallic glasses (MGs) still dramatically inhibits their widespread applications in wastewater remediation. Here, heterostructured catalysts were exploited by rapid annealing of Fe-based MGs and subsequent ball milling (BM) as advanced alternatives for amorphous counterparts in Fenton-like process. It was found that the surface characteristics tailored by ball milling enable more chemically active sites due to its enlarged specific surface area, surface defects and nanosized amorphous oxide layer that significantly enhance surface-catalyzed reaction in Fenton-like process. On the other hand, high-temperature annealing induced grain growth and electrochemical potential difference induced effect of galvanic cells in multiple crystalline phases (e.g. alpha-Fe (Si), Fe2B and Fe3Si) further provide an important contribution to high efficiency of electron transfer in heterostructured catalysts. Since the multiphase heterostructure is easily formed by a high-temperature annealing of MGs/amorphous-crystalline composite alloys, this work aims to provide an advanced alternative of MG catalyst without the elemental limitation of glass forming ability for wastewater remediation. (C) 2020 Elsevier Inc. All rights reserved.