Unlike thermal processes such as distillation, pervaporation relies on the relative rates of solute permeation through a membrane and is a combination of evaporation and gas diffusion. The analytical pervaporation systems consist of a membrane module suitable for liquid sample introduction and a vacuum (or a sweeping gas) on the permeate side. It has been used in a wide range of applications including the analysis of various organic and inorganic compounds, and sample concentration. It has been directly interfaced with gas chromatography, spectrophotometry, capillary electrophoresis, electrochemical detectors, liquid chromatography, and mass spectrometry. A wide range of liquids, slurries, and solids samples has been analyzed using these techniques. This review highlights the basic principles of the pervaporation and the state of its current development as applied to analytical chemistry.