Herein, we investigated in detail the relationship between surface properties and extraction performance of virgin and amino-functionalized MIL-101s(Fe) for the extraction of 10 bisphenols (BPs) and their derivatives. These BPs were used as model contaminants due to their different hydroxyl groups and contrasting polarities. The differential sorption efficiencies for relatively polar BPs (BPF, BPE, BPA, BPB, BPZ, BPAP and BPP) lies in the formation of hydrogen-bonding between –OH of target analytes and –NH2 of two MIL-101s(Fe). However, the surface properties of MIL-101(Fe) and NH2-MIL-101s(Fe), such as SBET and pore structure, determined the extraction recoveries for BPs derivatives (BADGE, BADGE·2H2O and BFDGE·2H2O) due to lack of –OH in their molecular structures. NH2-MIL-101s(Fe) nanosorbent was successfully applied to the preconcentration/extraction of trace BPs and their derivatives by dispersive solid-phase extraction (DSPE) method. Following optimization of the main factors, recoveries for BPs ranged from 90.8 to 117.8% and their LODs were 0.016–0.131 μg L−1 in environmental waters. Experimental precisions based on relative standard deviations were 0.9–4.9% for intra-day and 1.3–7.6% for inter-day analyses, respectively. These findings provide important information on how to design and modify nanosorbents for highly efficient extraction of pollutants having contrasting polarities. Moreover, the newly developed NH2-MIL-101s(Fe)-based DSPE method has a good application prospect in pretreatment of trace pollutants in real-world waters.