Magnetic multi-walled carbon nanotubes were prepared as magnetic solid-phase extraction (MSPE) adsorbent for the enrichment of six heterocyclic pesticides in environmental water samples, including imidacloprid, triadimefon, fipronil, flusilazole, chlorfenapyr and fenpyroximate. Then six heterocyclic pesticides were separated and determined by high-performance liquid chromatography-diode-array detector (HPLC-DAD). Major factors influencing MSPE efficiency, including the dose of mag-multi-walled carbon nanotubes (mag-MWCNTs), extraction time, solution pH, salt concentration, type and volume of eluent and desorption time were investigated. Under the optimized conditions, the enrichment factor of the method reached to 250. The linearity was achieved within 0.05-10.0 μg/L for imidacloprid and chlorfenapyr, 0.10-10.0 μg/L for fipronil, flusilazole, triadimefon and fenpyroximate. Limits of detection were in the range of 0.01-0.03 μg/L. Good precision at three spiked levels were 1.1-11.2% (intra-day) and 1.7-11.0% (inter-day) with relative standard deviation of peak area, respectively. The developed method was utilized to analyze tap water, river water and reservoir water samples and recoveries at three spiked concentration levels ranged from 72.2% to 107.5%. The method was proved to be a convenient, rapid and practical method for sensitive determination of heterocyclic pesticides.