Display omitted •Amorphous boron exhibited outstanding catalytic activity and superior stability for peroxymonosulfate activation.•Effective degradation of bisphenol S was achieved in the amorphous boron/peroxymonosulfate oxidative system.•The corresponding catalytic oxidation mechanism was elucidated. Recently, tremendous efforts have been devoted to developing carbon-based metal-free catalysts as an alternative to metal-based catalysts for remediation of emerging contaminants. However, further investigations have demonstrated that the durability of carbocatalysts is poor. Therefore, it is extremely desirable to seek a novel metal-free catalyst with high efficiency and superb stability. Herein, we first discovered that amorphous boron (A-boron) can be used as a metal-free catalyst for peroxymonosulfate (PMS) activation to produce free radicals for effective degradation of bisphenol S (BPS), which is a newly-occurring estrogenic endocrine-disrupting chemical. It exhibited outstanding catalytic activity and superior stability as comparing to metal-based and metal-free carbon-based catalysts. Moreover, many other typical organic pollutants in water such as bisphenol F, sulfamethoxazole, rhodamine B and methyl orange can also be effectively decomposed in A-boron/PMS oxidative system. The effects of reaction parameters on BPS degradation were systematically investigated. The catalytic oxidation mechanism was proposed. The intriguing catalytic feature of A-boron discovered in this study will provide new opportunities for the future development of A-boron based materials with promising applications in water remediation.