This work highlights the use of various types of ionic liquids (ILs) in microextraction techniques coupled to high-performance liquid chromatography (HPLC). In Chapter 2, magnetic ionic liquids (MILs) are used in headspace single-drop microextraction (HS-SDME) for the first time, where a rod magnet was employed to hold the MIL extraction phase. The use of magnetic force resulted in stable extraction phase during a long extraction time at high temperature conditions, overcoming the inherent disadvantage of traditional SDME method. In Chapter 3, polymeric ionic liquids (PILs) are employed as sorbent coatings for solid-phase microextraction (SPME) in high salinity sample matrix. Double-confined PIL coating was fabricated with monomer and crosslinker containing polymerizable cation and anion. The double-confined PIL fiber exhibited good extraction capabilities of ultraviolet filter compounds when high concentration of salt was present in the sample solution. The lifetime of the double-confined PIL fiber was much longer compared to that of commercially available PDMS/DVB fiber. The two methods highlighted in this thesis demonstrate the versatility of ionic liquids in sample preparation techniques and their future direction.