Functional hybrid silicas are potential materials for application in many areas of research.Two routes are mainly used to prepare these materials: (1) grafting a functional silane on a silica surface and (2) sol-gel hydrolysis of the functional silane precursor.Organotrialkoxysilanes are key precursors for their synthesis and many functional alkoxysilanes are commercially available such as 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane and n-alkyltriethoxysilane are the most commonly used to improve adhesion, abrasive strength, water repellency,etc...Although these silanes can further be post-functionalised with other groups but the reactions are not very clean and the purification of the products is often tedious.Organotrialkoxysilanes are moisture-sensitive and thus reactions that can be performed under anhydrous conditions to afford the compounds with easy purification steps are an absolute prerequisite.The click reaction via the copper-catalyzed alkyne azide cycloaddition reaction (CuAAC) in materials chemistry prompted us to envisage its use to link an organic function bearing a terminal triple bond with an azido-alkyltriethoxysilyl moiety.[1] A very fast and selective method was developed to produce organotrialkoxysilanes in quantitative yield and with high purity upon only simple extraction and filtration work-up procedures.Triethoxysilyl groups can be linked to challenging substrates, allowing the formation of new types of organotriethoxysilanes.In this presentation, I will describe the scope of this approach.In particular, I will focus on triethoxysilyl substrates containing functionalities (azide or terminal alkyne) that can undergo click reactions to give new functional organosilanes, precursors of hybrid silicas which can be used for several interesting applications such as optics, [2] catalysis [3] and drug carriers/delivery [4].