From the viewpoint of structural chemistry, structure and bonding lie at the heart of rational syntheses that have already contributed to many signi?cant scienti?c advances in inorganic chemistry and material chemistry, and especially to the discovery of some functional materials. Naturally the ?rst step to novel functional material is "synthesis", and in many cases exploratory synthesis seems to be the onlyworkableroutetonewcompound.However,rationalsynthesiswillsurelymake property-oriented exploration more fruitful and pleasing. Successundertheguidanceofelectronicstructuralfeatures,bondinginteractions, chemical reactivity of building units, etc. has been achieved in many systems. We have presented some signi?cant advances on ?ve topics via review-type chapters that were written by ?ve of the leading authorities in their ?elds. These chapters c- cern chemical approach to new quasicrystals, discovery of complicated compounds of pnicogen, the tuning of redox levels and oligomerization of triruthenium-acetate clusters, structural modi?cation of monomeric phthalocyanines, and the controlled assembly of amino lanthanide metal-organic frameworks (MOFs). Thisvolumehasshownthatthecontrolledassemblyandmodi?cationofinorganic systems are accessible and efforts along the way will contribute greatly to the discovery of new functional materials as well as the satisfaction of the curiosity of fundamental research.