A novel tetradentate amine ligand namely N,N,N ',N '',N ''',N '''-hexaoligo (ethylene glycol) triethylenetetramine (HOEGTETA) was employed in the homogenous ATRP of MMA in anisole using CuBr and CuBr2 as the catalyst and ethyl 2-bromoisobutyrate (EBiB) as an initiator. The effect of the polymerization temperature and the various ratios of Cu(I) to Cu(II) were investigated in detail. Moreover, we demonstrated the ATRP of MW by using only Cu(II) in the absence of any free radical initiator, reducing agent, or air. The ATRP of MMA with the use of only Cu(II) and HOEGTETA or N,N,N ',N '',N ''-pentamethyldiethylenetriamine (PMDETA) resulted in well-defined PMMA. [GRAPHICS] 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