The reactions taking place during voltametric cycling of manganese oxides can be determined using in situ Raman spectroscopy. The main difficulty for the oxide identification is to obtain relevant Raman reference spectra because of the many possible compounds and, for some of these compounds, of their instability in the laser beam. As a consequence, several modifications of different tetra‐, tri‐ and divalent manganese oxides and oxyhydroxides were carefully studied. The electrochromic behavior of three types of manganese oxides, two prepared by thermal oxidations and the other by electrochemical deposition, were then compared. The presence of nonstoichiometry in the pristine material was necessary to obtain a reversible electrochromic effect. The reaction during electrochromic cycling is more complicated than a simple passage from to .