In the search for alternative inert surfaces replacing silicon chips in Desorption/Ionization On porous Silicon (DIOS)-like mass spectrometry analyses, nanostructured silicon-based NALDITM chips were evaluated in Laser Desorption/ionization (LDI) of peptides. Comparisons were made using commercially available DIOS chips (MassPREPTM-DIOS-targetTM), amorphous carbon powder from lead pencil and porous silica gel used for chromatographic purposes as reference supports. A set of synthetic model peptides presenting variable amino acid sequences of various lenghts was analyzed under all conditions. The LDI responses of the four 'matrix-free' techniques were compared, especially in terms of peptide detection sensitivity and overall experiment robustness.