AbstractH‐bonding in ionic hydration is crucial for understanding various phenomena such as osmolyte effects, ion transport, electrochemical processes, etc. Ionic liquids (ILs) from the biomaterials have great affinity for protein solubility and stabilization due to hydrophobicity and hydrogen bonding ability. To explore potential use of ionic liquids, it is essential to understand hydration of ionic liquids with detailed information on H‐bonding within the water of hydration. In this context, near‐infrared spectral investigation of H‐bonding in water of hydration of 1‐n‐alkyl‐3‐methylimidazolium bromides and 1‐ethyl‐3‐methylimidazolium based amino acid ionic liquids were made through simultaneous estimation of hydration number and hydration spectra of ILs in the spectral range of 7800‐5800 cm−1. Weak H‐bonding extist in the water of hydration for 1‐n‐alkyl‐3‐methylimidazolium bromides while strong cooperative H‐bonding exists in case of amino acid ionic liquids leading to higher hydration numbers. The results further demonstrate that the individual resolved spectral components can be used to analyse (qualitatively and quantitatively) different types of H‐bonded species at ionic surfaces. Along with all these, the effect of hydrophobicity on hydration behavior as well as on the nature and strength of H‐bonding within the hydration shell of ions are also probed and discussed.