Nanoporous Si was obtained by means of metal-assisted chemical etching. Li ion insertion–extraction was tested by voltammetric and galvanostatic electrochemical cycling in conventional 1 M LiPF6 ethylene carbonate/dimethyl carbonate EC/DMC and in 1 M LiTFSI 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethyl) sulfonylimide [BMP] [TFSI] electrolytes. The nanoporous Si demonstrated high reversibility when cycled in 1 M LiPF6 EC/DMC electrolyte and showed superior activity compared to the non-structured sample. In contrast to the organic carbonate electrolyte, the material cycling in ionic liquid media showed reduced capacity and reversibility of the Li ion exchange. The latter results were discussed in terms of the high viscosity of the ionic liquid and ineffective cathodic passivation of the Si substrate in the ionic liquid-based electrolyte. Scanning electron microscopy imaging showed minor morphological changes due to the large volume change during Li insertion. No signs of crack formation and propagation were detected during the time span of the measurement.