Airborne particulate matter is well known because of its adverse impacts on human health and its role in climate processes. The chemical composition of atmospheric aerosols is of basic importance. Chemical analysis of aerosols involves broadly two steps, extraction step and detection/quantification of chemical constituents. Generally aerosols are extracted using classical techniques which, have many disadvantages. This dissertation addresses the use of both classical extraction methods and liquid membrane based extraction as a sample preparation steps for aerosols analysis. Common techniques that are used for this purpose are not environmentally green as they involve a lot of organic solvent, they are not efficient and selective enough and do not serve the purpose of trace level analysis as they do not give sufficiently high enrichment. We have shown that hollow fiber liquid phase microextraction (HF-LPME), which is environmentally green is applicable to aerosol samples. Both two-phase and three phase HF-LPME are very helpful in pre-concentration of analytes from aerosol. The dissertation summarises the results of our research for the last four years.