A novel carbon nanoparticles-coated solid-phase microextraction (SPME) fiber was prepared via a simple and low-cost flame-based preparation process, with stainless steel wire as support. Surface characteristic of the fiber was studied with scanning electron microscope. A nano-scaled brushy structure was observed. Coupled to gas chromatography (GC), the fiber was used to extract phthalate esters (PAEs) and polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Analytical performances of the proposed method were investigated under the optimum extraction conditions (extraction temperature, 40°C; content of KCl, 30% (w/v); extraction time, 50min for PAEs and 40min for PAHs) and compared with other reports for the same analytes. Calibration ranges were 0.06-500μgL(-1) for di-n-butyl phthalate (DBP), and 0.1-300μgL(-1) for di-cyclohexyl phthalate (DCHP) and di-(2-ethyl-hexyl) phthalate (DEHP). For the eight PAHs, good linearity was obtained ranging from 0.01 to 150μgL(-1). Limits of detection were 0.005μgL(-1) for three PAEs and 0.001-0.003μgL(-1) for eight PAHs. The fiber exhibited excellent stability. It can be used for 100 times with RSDs of extraction efficiency less than 22.4%. The as-established SPME-GC method was applied to determine PAEs in food-wrap and PAHs in cigarette ash and snow water, and satisfactory results were obtained. The carbon nanoparticles-coated SPME fiber was efficient for sampling of organic compounds from aqueous samples.