A novel alumina hollow fiber was synthesized by sol-gel template method and was characterized by scanning electron microscopy. N-2 adsorption technique and X-ray diffraction. With the use of prepared alumina hollow fiber as extraction membrane, a new method of flow injection (FI)-membrane solid phase microextraction (MSPME) on-line coupled to inductively coupled plasma-optical emission spectrometry (ICP-OES) was developed for simultaneous determination of trace metals (Cu, Mn and Ni) in environmental water samples. The adsorption capacities of the alumina hollow fiber for Cu, Mn and Ni were found to be 6.6, 8.7 and 13.3 mg g(-1), respectively. With a preconcentration factor of 10, the limits of detection (LODs) for Cu, Mn and Ni were found to be 0.88, 0.61 and 0.38 ng mL(-1), respectively, and the relative standard deviations (RSDs) were ranging from 6.2 to 7.9% (n = 7, c 10 ng mL(-1)). To validate the accuracy, the proposed method was applied to the analysis of certified reference material GSBZ50009-88 environmental water and the determined values are in good agreement with the certified values. The developed method was also employed for the analysis of Yangtze River water and East Lake water, and the recoveries for the spiked samples were in the range of 87.4-110.2%. (C) 2011 Elsevier B.V. All rights reserved.