In the present work, we reported a structural investigation of liquid ethylene glycol (EG) at 298K and atmospheric pressure via neutron scattering and DFT calculation. Original scattering data at large scattering wave vectors were analyzed to deduce the structure factor SM(q), the molecular form factor F1(q) and the intermolecular pair correlation function gL(r). A large variety of hydrogen-bonded dimers and trimers has been considered in order to describe the intermolecular arrangement of the liquid EG. Natural bond orbital (NBO) and atoms-in-molecules (AIM) analyses have been performed to get insight about the nature of hydrogen bond between EG molecules. Complete vibrational assignments and analysis of fundamental modes of the more probable clusters were performed on the basis of potential energy distribution (PED) calculations and the available experimental infrared and Raman spectra in the liquid phase.