Imidazole (C₃H₄N₂) is an important biomaterial for material research and applications. Our high-pressure Raman spectroscopic investigations combined with ab initio calculations on crystalline imidazole suggest that C−H---X (X = N,π) and N−H---N intermolecular hydrogen bonding interactions largely influence the nature of its structural and polymeric transformations under pressure. At pressures around ∼10 GPa, the reduction in the N---N distances close to the symmetrization limit and the emergence of the spectral features of the cationic form indicate the onset of proton disorder. The pressure-induced strengthening of the “blue-shifting hydrogen bonds” C−H---X (X = N, π) in this compound is revealed by the Raman spectra and the ab initio calculations. No polymer phase was retrieved on release from the highest pressure of 20 GPa in this study.