Nanocasting strategy is here proposed as effective approach to tune structure and size of α-Fe 2 O 3 active nanoparticles as a promising anode material for Li-ion cells. MCM-41 and MCM-48 silicas, presenting hexagonal 2D and cubic 3D symmetry, respectively, and regular pore diameter of about 4nm are selected as moulds. The structural–morphological and electrochemical characteristics are assessed by X-ray diffraction, transmission electron microscopy, N 2 physisorption at 77K, cyclic voltammetry and galvanostatic discharge/charge cycling. It is here demonstrated that structural–morphological features change accordingly to the template used and careful control of the texture/particle characteristics is likely a fundamental variable noticeably affecting the cycling behaviour.