A review is presented here of the crystal chemistry of natural silicates of alkaline elements, mainly Na, with a focus on reporting recent data on the structural mineralogy of the new members of this chemical family and their crystal structures. The majority of the natural hydrous silicates of alkaline elements studied are characterized by a specific crystal-chemical feature − the presence of silanol groups Si−OH. The discovery of the two new minerals, chesnokovite and yegorovite, means that all the main topological types of the [SixOy] complexes are represented in the crystal structures for this family.