The degree of crystallinity, morphology and electrochemical properties of a nanocomposite formed by stabilized alpha-Ni(OH)2 nanoparticles and bentonite nanoflakes is strongly influenced by the vacuum drying process, either at room temperature or by freeze-drying (lyophilization). Alpha-Ni(OH)2 nanoparticles induced the formation of intercalation nanocomposites exhibiting higher structural organization than in the precursor clay. Also, lyophilization process preserved the structure of the nanocomposites in aqueous suspension and/or induced the disaggregation of nanoflakes, producing materials with lower degree of crystallinity, larger interlamellar distances and electrochemically more active than those obtained by conventional vacuum drying. In fact, the lyophilized materials exhibited more than twice as large density of current for electrocatalytic oxidation of methanol (37 against 14 mA cm−2) indicating its potentiality for development of sensors and fuel cells.