Oxide-covered aluminium electrodes were used to demonstrate that aromatic compounds, such as the simple derivatives of benzene, can be electrochemically excited at cathodically pulse-polarized conductor/insulator/electrolyte (C/I/E) tunnel junction electrodes (e.g. oxide-covered aluminium electrodes). The primary cathodic process at these electrodes was a tunnel emission of hot electrons into an aqueous electrolyte solution. Fluorescence (FL) and electrochemiluminescence (ECL) spectra were compared and the dependence of the electrochemiluminescence on the concentrations of benzene, toluene, phenol, p-cresol and aniline were measured and detailed mechanisms for the present electrochemiluminescence are proposed.