In this paper, we present a novel method to study the electronic density-of-states of intercalation materials. We present evidence that electrochemical quasi-steady state potential curves of a number of materials exhibit fine structure in striking agreement with the density of electronic states, as obtained from ab initio calculations. The ability to probe the electronic structure by our electrochemical technique seems, in most cases, to be restricted to disordered materials. We suggest that localization of the band states is essential, in order for the technique to give a good picture of their density. The electrochemical density of states is often smaller than the computed one due to kinetic effects, i.e. very slow relaxations of the charge carriers. Our highly sensitive electrochemical method opens new vistas for studying the electronic structure of disordered materials, that can be intercalated with an ionic species.