This review summarizes recent developments in the area of heteroatom-based dendrimers, i.e., dendrimers whose connectivity is based on atoms other than carbon. Hyperbranched structures based on heteroatoms are also considered to a limited extent. In addition, the potential that such dendrimers offer to materials science and how this class of materials can be exploited for the rational design of ordered molecular materials is discussed. Three main classes of heteroatom-based dendrimers are distinguished: i) dendrimers based on group IV elements, such as Si or Ge, as branching points; ii) dendrimers based on phosphorus as branching atom; iii) dendrimers that are assembled via transition-metal complexes.