A simple and sensitive method for the determination of polar aromatic amines (PAAs) was developed using stir bar sorptive extraction (SBSE) coupling to high-performance liquid chromatography. A hydrophilic poly(vinylimidazole-divinylbenzene) (VIDB) monolithic material was prepared and acted as SBSE coating. The influences of polymerization conditions for VIDB on the extraction efficiency were investigated using aniline and 2,4-dinitroaniline as detected solutes. To achieve optimum extraction performance for PAAs, several parameters including extraction and desorption time, desorption solvent, ionic strength and pH value of sample matrix were investigated. The results showed that under the optimized experimental conditions, the method showed good sensitivity and excellent recoveries, as well as advantages such as linearity, simplicity, low cost and high feasibility. The extraction performance of present method to the target compounds also compared with commercial SBSE which using polydimethylsiloxane as coating and other SBSE which based on monolithic materials. Finally, the proposed method was successfully applied to the determination of PAAs in lake and sea waters, and excellent recoveries of spiked target compounds in real samples were obtained.