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Base on the previous work in laboratory, a novel polyaniline doped with polydimethylsiloxane coating was developed on a stainless steel wire for solid phase microextraction(SPME) by electroplating method. This electroplating method not only has advantages of ease preparation and simple equipments required, but also increases the lifetime of the SPME fiber. The composite fiber ( polyaniline/polydimethylsiloxane(PANI/PDMS) ) was evaluated by analyzing n-tridecane, n-tetradecane and n-pentadecane in aqueous sample. The new fiber coating showed comprehensive abilities to extract alkanes compounds. The relative standard deviations were found to be 6.8%-10.33%.