Raman scattering spectroscopy have been applied to the study of local structure of Li4/3Me5/3O4 (Me = Ti, Mn) spinel oxides used as electrode materials for rechargeable lithium batteries and hybrid supercapacitors. We report the analysis of their vibrational spectra using both the classical factor group analysis and a local environment model. Electrochemical performance was carried out using a lithium cell with solvent-free solid-polymer. Raman spectra of Li4/3+x Me5/3O4 spinels are compared and analyzed on the basis of structural modifications of their lattices upon lithium insertion.