Synthetic approaches to new materials are as various as the nature of the materials themselves. Here, we report on one synthetic concept that was used during the recent past to address a variety of different families of compounds from superionic conductors and supersphere cages for molecular trapping to new white-light generators and reactive multimetallic clusters. The use of small binary molecules comprising atoms of two main group elements is the base of all of the presented methodologies, which lead to the named classes of materials according to the choice of the elemental combination and the specific reaction conditions.