The ether-functionalized imidazolium ionic liquids (IL) applied in the silica sol-gel process demonstrated a defined coordination potential. These IL display the capacity to control the system organization from the reactions' first moments through a dynamic system-assembling ability, being the sum of ionic and physical interactions, i.e. Coulomb forces, H-bonding and London forces. The initial hydrolysis steps of tetraethyl orthosilicate (TEOS) in the presence of these IL were followed by Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering (DLS), both in time-resolved experiments, in an attempt to correlate the structuring and the bonding dynamics of these systems. (C) 2015 Elsevier Inc. All rights reserved.