Because of its sensitivity to chemical and electrostatic characteristics, nitrite group as an infrared (IR) probe to monitor the local structure, folding kinetics, and electrostatic environment of protein, or solvation of molecular solvents, has attracted increasing attention. Herein, by choosing benzonitrile and imidazolium ionic liquids (ILs) as the IR probe and model ILs, respectively, we report that the nitrile stretching vibration (nu CN) could be utilized as a simple and substantial IR probe to monitor the local environment of ILs such as hydrogen bonding (H bonding) as well as intrinsic electric field. In 1-alkyl-3-methylimiclazolium-based non hydroxyl ILs, the nu CN is in a "free" state, and is less affected by the alkyl chain, while it significantly decreases with the effective anion charge. In 1-(2-hydroxyethyl)-3-methylimidazolium-based hydroxyl ILs, however, a distinct anion dependent nu CN forming H-bonding with the hydroxyl is also observed besides the "free" nu CN band. The "free" component of nu CN can be further employed to determine the intrinsic electric field in both non-hydroxyl (directly) and hydroxyl (indirectly by subtracting H-bonding contribution) ILs by using vibrational Stark effect. Moreover, the result suggests that benzonitrile is preferentially located in the charge domain in ILs and it could be a more suitable probe to report the ionic network rather than the nonpolar domain in ILs.