The extractability of some typical environmental pollutants in ionic liquids (ILs) was screened by using a simple one-step liquid phase microextraction procedure. It was demonstrated that 1-alkyl-3-methylimidazolium hexafluorophosphate ([CnMIM][PF6], n = 4, 8), two typical ILs, could effectively extract a set of 45 typical environmental pollutants including BTEX (benzene, toluene, ethylbenzene, and xylene), polycyclic aromatic hydrocarbons, phthalates, phenols, aromatic amines, herbicides, organotin, and organomecury. Analytes in 10 mL sample solution held in a 15 mL vial were extracted by a 5 microL drop of ILs suspended on the needle of a high-performance liquid chromatography (HPLC) microsyringe; this was followed by HPLC, atomic absorption spectrometry, or cold-vapor atomic fluorescence spectrometry determination. The enrichment factors determined were in the range of 5-168 for 15 min extraction by [C4MIM][PF6] and 4-178 for 30 min extraction by [C8MIM][PF6], respectively, which indicates that ILs might be considered as potential environmentally benign alternative recyclable solvents for the enrichment of environmental pollutants.