The liquid-phase microextraction (LPME), based on disposable hollow fiber, has been developed to be a new environmentally benign sample preparation technique which incorporate sampling, extraction and concentration into a single step. The novel technique can be easily manipulated in combination with high performance liquid chromatography, gas chromatography and capillary electrophoresis, and can provide excellent sample clean-up effect and high degree of extraction recovery and enrichment. It is proved to be simple, low-cost and virtually solvent-free. The extraction set-up, extraction mode, basic principles and recent applications of the hollow fiber-based liquid-phase microextraction are reviewed.