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The unintended leakage of endocrine-disrupting bisphenol A (BPA) from different industries into the aquatic environment has posed a severe threat to aquatic lives and human health. Herein, we explored a hydrothermal method to synthesize superparamagnetic β-cyclodextrin-cobalt ferrite (β-CD-CoFe2O4) catalyst for the selective capturing and efficient degradation of BPA through heterogeneous activation of peroxymonosulfate (PMS). The as-prepared catalysts were systematically characterized through multi-techniques to explore the relationship between their catalytic performance and material properties. Results showed that, in β-CD-CoFe2O4/PMS system, the degradation rate of BPA reached 99.23% in 60 min with a rate constant of 0.0708 min−1, approximately 16.09 times than CoFe2O4/PMS system (0.0044 min−1). Specifically, the large surface area and availability of more reactive sites of β-CD-CoFe2O4 boosted the activation process of PMS compared to pristine CoFe2O4, thus enhancing the degradation of BPA. Meanwhile, the effect of different operational parameters and co-existing anions on BPA degradation were also investigated. The generation of free radicals ( S O 4 ∙ - , ∙ O H , O 2 ∙ - , a n d 1 O 2 ) in the β-CD-CoFe2O4/PMS system liable for reducing BPA was corroborated through electron paramagnetic resonance analysis and quenching experiments. The possible degradation pathways of BPA were proposed based on the identification of reaction intermediates formed during the mineralization process. In brief, the findings of this study suggested that β-CD-CoFe2O4 is an efficient and environmentally friendly catalyst that facilitated the degradation of BPA through PMS activation. Moreover, the excellent magnetic separation, stability, and reusability of the β-CD-CoFe2O4 catalyst make them promising candidates for their water purification applications.