Discovering new catalytic applications of Fe-based metallic glasses (MGs) besides the decolorization of azo dyes is an active topic. In this article, two types of coke wastewater before anaerobic treatment (I) and after aerobic treatment (II) are applied to investigate the catalytic performance of Fe78Si8B14 and Fe73.5Nb3Cu1Si13.5B9 MGs in Fenton-like system. The experimental parameters, including hydrogen peroxide concentration, temperature and solution pH are detailed studied. The Fe78Si8B14 MGs exhibit a superior catalytic capability in wastewater treatment compared with the Fe73.5Nb3Cu1Si13.5B9 MGs. The Fe73.5Nb3Cu1Si13.5B9 MGs provide less reactive sites and lower Fe content in the coke wastewater due to the inclusion of Nb, restricting the generation of hydroxyl radicals and hindering the degradation reaction. The chemical oxygen demand removal efficiency of the wastewater I and II treated with Fe78Si8B14 MGs could achieve 71% within 30 min and 89% within 60 min under the optimal condition, respectively. These results expand the practical applications of Fe-based MGs in treating environmental pollutants.