Estrogens and bisphenols are typical endocrine disruptors (EDs) that pose a potential hazard to the human body due to their widespread presence in aqueous environments. In this study, a β-cyclodextrin porous crosslinked polymer (β-CD-PCP) was prepared in-situ on a glass fiber surface by a nucleophilic substitution reaction. An effective and sensitive solid phase microextraction method using functionalized glass fiber with β-CD-PCP coating as the adsorbent was established for the detection of 11 EDs in a water environment. The β-CD-PCP was in-situ prepared on a glass fiber surface by a nucleophilic substitution reaction. The β-CD-PCP successfully separated five estrogens (ESTs) and six bisphenols (BPs) through hydrophobic and π-π interactions. The conditions affecting extraction were optimized. Under the optimized conditions, the ESTs obtained a high enrichment effect (1795–2328), low limits of detection (0.047 µg L−1) and a good linearity range (0.2–15.0 µg L−1). Furthermore, the spiked recoveries of analyte ESTs in aqueous environments were between 82.9–115.7 %. The results indicated that the prepared functionalized glass fibers exhibited good adsorption properties, and the established analytical method was reliable for monitoring trace ESTs and BPs in aqueous environments.