This book is aimed to provide an alternate synthetic protocol for the synthesis of desired ordered complexes and networks where a coordination complex has been used as the building block. We demonstrate that how simple ligands selectively coordinate a central or primary metal ion while leaving the appended functional groups as the peripheral secondary binding sites. These secondary binding sites upon coordination to metal ions afford heterometallic complexes as well as networks of highly ordered nature. The book starts with the introduction to the metalloligands as the molecular building blocks and their application in the generation of coordination bond based self–assembled structures and networks. A detailed literature investigation supported with the discussion of important examples has been contained in the first introductory chapter. The remaining chapters have discussed in detail the synthesis, characterization and utilization of coordination complexes as the building blocks to generate ordered molecules and networks.