Copper-catalyzed azide-alkyne cycloaddition (CuAAC), combined with the chemical stability of the SiÀC-bound organic layer, serves as an efficient tool for the modification of silicon substrates, particularly for the immobilization of complex biomolecules. This review covers recent advances in the preparation of alkynyl-or azido-terminated "clickable" platforms on non-oxidized silicon and their further derivatization by means of the CuAAC reaction. The exploitation of these "click"-functionalized organic thin films as model surfaces to study many biological events was also addressed, as they are directly relevant to the on-going effort of creating siliconbased molecular electronics and chemical/biomolecular sensors.