Suitably activated, (Cp*){N(Bu-t)C(Me)N(Et)}ZrMe2 is known to initiate the 'living' and isotactic-selective polymerization of alk-1-enes, and it can be used to synthesize block copolymers and stereoblock polymers. We report a full molecular kinetic investigation of propene, but-1-ene, and hex-1-ene polymerization with a MAO-activated catalyst system. By combining NMR microstructural polymer analysis with OM modeling of the active species, the complicated regio- and stereochemistry of the polyinsertion process, as well as the active chain-transfer pathways, are investigated. The perspectives and limitations of this catalyst for application in (stereo)block polymerizations are discussed. [GRAPHICS] n. After in situ reduction, a large number of metal-based functional materials can be prepared. PVP is alkaline, and thus capable of catalyzing the sol-gel process to generate an inorganic shell. Furthermore, pre-formed nanoparticles can also be absorbed by the shell through specific interactions. The PS core is not infiltrative during synthesis, and hollow rings can be derived after the polymer templates are removed. [GRAPHICS] b