A novel solid-phase microextraction (SPME) fiber was prepared by coating multiwalled carbon nanotube (MWCNTs) on a stainless steel wire, and its characteristics were studied. To evaluate the MWCNTs coating, the fiber was used for the extraction of some organochlorine pesticides (OCPs) from water samples by Headspace SPME (HS-SPME) mode. Potential factors affecting the extraction efficiency such as extraction time, extraction temperature, agitation, ionic strength, desorption temperature, and time were also optimized. Several experiments were carried out by water spiked with target compounds to evaluate the analytical characteristics of the proposed method under optimized conditions. The linearity was from 0.1 to 10 ug/L with the linear correlation coefficients (r) ranging from 0.9956 to 0.9995. The limits of detection (LOD, S/N ¼ 3) for these pesticides were between 0.43 and 2.13 ng/L and the precision (RSD, n ¼ 5) was 2.53-12.25%. When this method was applied for the spiked real river sample, the relative recoveries ranged from 72.4% to 134.7% for the tested OCPs.