The PhD project aims in tracing the structural pathway of liquid metals to vitrification and revealing the structural origin of the remarkable slowdown of the dynamics occurring in the super-cooled liquids that leads to the formation of glasses. How the atomic structure of metallic liquids evolves during rapid quenching is currently not well understood. This limitation is largely attributed to the experimental times for the acquisition of diffraction data being longer than the short quenching times required for vitrification, and thus hindering in-situ structural measurements. A sophisticated approach will be used to overcome these limitations and study the structure of metallic liquids, super-cooled liquids and glasses using state of the art structural characterization techniques and modelling including high energy synchrotron radiation and containerless solidification methods. This PhD project includes the structural analysis of the liquid, super-cooled liquid and glassy states of glass forming alloys using X-ray Diffraction, pair and radial distribution function and electron microscopy. Molecular Dynamics and Reverse Monte Carlo Simulations will be employed to provide insights of the evolution of the local geometrical atomic arrangements in the liquid and the glassy structures and will be compared with the experimental results.