The results obtained with solid electroactive microparticles immobilized on a graphite electrode surface using cyclic voltammetry and in situ microRaman measurements at selected potentials allowed us to complete the understanding of the spectroelectrochemical behaviours of Prussian blue, β-PbO and Bi2O3. In the case of Prussian blue, we provided a simple but complete analysis of the Raman spectral data for the species Fe[Fe(CN)6] and K2Fe[Fe(CN)6]. The investigation of PbO in neutral chloride media showed that Pb(OH)Cl is the Pb° electrochemical oxidation product whereas the study of Bi2O3 demonstrated that the oxidation of Bi° in alkaline solutions leads essentially to amorphous Bi(OH)3.