With the use of various electrodeposition conditions (concentration and pH of the bulb MnSO4 solution, temperature, synthetic mode) and thermal treatments, gamma-MnO2 materials exhibiting rather different physico-chemical and structural characteristics were prepared. Relationships were established between synthesis conditions and such characteristics, showing that to some extent, these physico-chemical and structural parameters can be tuned. The electrochemical behavior of lithiated phases obtained upon the first Li insertion into these gamma-MnO2 materials has been investigated. It is shown that the maximum Li reversible intercalation capacity strongly depends on the structural parameters (concentration of De Wolff defects and degree of microtwinning) of the starting gamma-MnO2 samples.