Alkaline silicates are well-known soluble silica derivatives already widely used for industrial purposes. Nevertheless, their applications for the elaboration of functional optical coatings have largely been discarded by the sol-gel community who mainly focused on alkoxide precursors. The objective of this work is to reconsider the alkaline silicates sol-gel chemistry, targeting optical coatings of a few hundreds of nanometers. The structures of Li+, Na+, and K+ silicate coatings are discussed on the basis of spectroscopic characterizations. We show that a simple washing process allows a postdeposition removal of most alkaline ions, thus preventing the efflorescence effect and improving the aqueous stability of the films. Finally, several examples are shown for the application of alkaline silicates in the elaboration of functional optical coatings following conventional sol-gel chemistry.