A method based on combination of solid- and liquid-phase microextraction was developed, porous CuO nanostructures were created on the surface of the copper wire by electrochemical process and used as extractant solvent holder. Isoamylbenzoate was immobilized in the pores of CuO coating and applied for microextraction of benzene, toluene, ethylbenzene and xylens from aqueous samples followed by gas chromatography- flame ionization detector. The experimental parameters such as the type of organic solvent, salt concentration, extraction temperature, extraction time, desorption temperature and desorption time, were investigated and optimized. Under optimum conditions, the method detection limits were between 0.4 and 0.6 ?g/L. The relative standard deviation of the method for the analytes at 5-100 ?g/L concentration level ranged from 1.0 to 15%. The fiber-to-fiber reproducibility for three fibers prepared under the same condition was from 2.0 to 13%. River and well water samples analyzed for the evaluation of the method in real sample analysis. Relative recoveries for spiked tap and river waters samples were in range of 73.0-118.0% and relative recoveries for spiked wastewater were in range 13.0-71%. In addition, the method was compared with a commercial solid phase microextractio (SPME) fiber.