The preparation of composite layers made of porous silicon (PS) infiltrated with nanostructured carbon is reported. These composite layers were obtained by chemical vapor infiltration (CVI) of mesoporous silicon under process conditions normally employed to grow diamond films by Hot Filament Chemical Vapour Deposition (HFCVD). Micro-Raman spectroscopy and Field Emission Gun Scanning Electron Microscopy (FEG-SEM) techniques showed that diamond nucleation density was very low whilst sp2 carbon permeated completely, even after 1 h deposition, the thickness of the PS layers that preserved their mesoporous columnar structure.