Nanocrystalline diamond (NCD) films were formed on porous silicon (PS) substrate by Chemical Vapor Deposition/Infiltration (CVD/CVI) process using a hot filament reactor. This innovative procedure is determinant to grow a controlled three-dimensional diamond structure with diamond grains formation in the pores, covering uniformly the different growth planes. In this CVI process, a piece of reticulated vitreous carbon (RVC) was used, under de PS substrate, as an additional solid source of hydrocarbon that ensures the production of pertinent carbon growth species directly on PS and into its pores. PS substrates were obtained by anodization etching process of n-type silicon wafer in a hydrofluoric acid (HF) solution containing acetonitrile (CH3CN) which result in an uniform and well controlled porous distribution and size when compared with the usual ethanol solution. Depositions were performed using Ar-H2-CH4 where the methane concentration varied from 0 up to 1.0 vol%, to analyze the influence of RVC use as an additional carbon source on growth mechanism. Scanning Electron Microscopy (SEM) and Field Emission Gun (FEG) were used to investigate PS and NCD film morphology. SEM images of NCD showed faceted nanograins with average size from 5 to 16 nm and uniform surface texture covering all the supports among the pores resulting in an apparent micro honeycomb structure. Raman spectra confirmed the existence of sp2-bonded carbon at the grain boundaries. The spectra showed a peak that may be deconvoluted in two components at 1332 cm(-1) (diamond) and 1345 cm(-1) (D band). Two shoulders at 1150 and 1490 cm(-1) also appear and are assigned to transpolyacetylene (TPA) segments at the grain boundaries of NCD surfaces. In addition, X-ray diffraction analyses of all films presented characteristic diamond diffraction peaks corresponding to (111), (220) and (311).