The effect of Mg-doping and Li overstoichiometry on the structural stability of LiCoO2 powders has been investigated with emphasis to voltammetric properties. Microparticle cyclic voltammetry (CV) conducted in caustic NaOH to best simulate a non-aqueous electrolyte shows a marked improvement of the structure stability of doped LiCoO2. In contrast to the unsubstituted LiCoO2 sample which shows voltammetric peaks associated to the well-known two-phase domain and monoclinic distortion reactions, in Li1.08Mg0.06CoO2, LiMg0.06CoO2 and Li1.08CoO2 samples these peaks are strongly suppressed providing direct evidence for the existence of a stable solid solution with negligible phase transitions in the reversible intercalation region (3.8–4.2 V vs. Li) as well as in the overcharged region. The effect is higher with Mg-doping, irrespective of the Li overstoichiometry. However, the concomitant presence of Mg and Li excess in the structure is important for obtaining small particle sizes. Since Mg-doping induces a quasi metallic behavior in the samples, whereas the Li excess may provide an higher initial capacity, it is suggested that the Li1.08Mg0.06CoO2 composition may be of interest as positive cathode for advanced Li-ion batteries.