Energy storage technologies that can meet the unprecedented demands of a sustainable energy system based on intermittent energy sources require new battery materials. In recent years, new superionic conducting glasses have been discovered that have captured the attention of the community due to their potential use as solid electrolytes for all-solid-state Li-ion batteries. New research is needed to understand the correlations between the non-crystalline structure of glasses and their advanced properties. Here we investigate the structural properties, the electronic structure and the electrochemical stability against Li metal of the high ionic conducting Li3ClO glass. We use the stochastic quenching method based on first principles theory to model the amorphous structure of the glass. We characterise the structure by means of radial distribution functions, angle distributions functions, bond lengths and coordination numbers. Our calculations of the electronic structure of Li3ClO for both phases, crystalline and amorphous, demonstrate that both materials are good insulators. We assess the electrochemical stability of the electrolyte against Li metal electrode and in particular we analyse the role of amorphisation. Our results show that crystalline Li3ClO is not stable against Li metal electrode and that the glass can be made stable if less oxygen is supplied, for instance, by producing an substoichiometric glass.