Two typical brominated flame retardants (BFRs), namely, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), were persistent organic pollutants widely detected in various environmental media. This study aimed to successfully synthesize micro-nano-structured magnetite particles (MNMPs) with surface modification by citric acid molecules. The synthesized composites served as an adsorbent for extracting TBBPA and HBCD from environmental water samples followed by gas chromatography-mass spectrometry analysis. The obtained MNMPs were characterized in terms of crystal structure, morphology, size distribution, hydrophobic and hydrophilic performance and magnetism. The results indicated that the MNMPs exhibited high surface area, good dispersibility, and strong magnetic responsiveness for separation. The parameters affecting the extraction efficiency were optimized, including sample pH, amount of sorbents, extraction time and desorption conditions. Under the optimum conditions, the recovery was 83.5 and 107.1%, limit of detection was 0.13 and 0.35μg/mL (S/N = 3), and limit of quantification was 0.37 and 0.59 μg/mL (S/N = 10) for TBBPA and HBCD respectively. The relative standard deviations obtained using the proposed method were less than 8.7%, indicating that the MNMP magnetic solid-phase extraction method had advantages of simplicity, good sensitivity and high efficiency for the extraction of the two BFRs from environmental water.