One future vision in macromolecular materials of industrial importance aims towards efficient synthesis protocols to produce economically large quantities of polymers with a high information content (e.g. perfectly controlled multi-block copolymers), which then afford functional construction components by self-assembling. One obvious route to this vision is certainly found in catalytic polymerization strategies. The rare-earth-metal catalyzed group transfer polymerization (REM-GTP) is shown to act as an extremely volatile route to produce polar polymers based on catalyzed and living poly(Michael addition) reactions. Insight into the thermodynamics of this polymerization is give and the ability to convert monomers ranging from CO2 over conventional monomers to novel Michael types, like vinyl phosphonic esters is shown. As a recent finding main-group-element catalysis, based on aluminum(III) organometallic compounds is discussed for important monomers, like acrylonitrile, which is a base for carbon fibers.