New enabling chemistries have been developed to produce novel well-defined polymeric materials through the additions of small amounts of reactive functional compounds to standard polymers during regular processing steps. We found that carbonyl biscaprolactam and its derivatives couple polymer chains in a strictly linear fashion. The requirements for fast and well-controlled coupling reactions, a prerequisite to apply this modular concept, were met. The breakthrough to produce a wide variety of novel polymers came when we found that many building blocks, provided with functional groups and blocked isocyanate groups, could be made on the basis of this chemistry. Blocked isocyanate groups are very suitable coupling units to fix desired functions onto polymer backbones. In one example, antifouling coatings were prepared by introducing fluorine groups. In another case, blocked isocyanate functional acrylates were built into a polyacrylate to make self-crosslinkable coatings. In another illustration, the concept was demonstrated by a novel route to prepare polyrotaxanes from rotaxane monomers provided with blocked isocyanates as polymerizable stopper groups. These reactive functional compounds gave, in a controlled manner, polymeric materials with substantially improved properties.