Multifunctional microgel-core star polymers with ruthenium catalysts are designed as catalyst-bearing nanoreactors to improve activity, controllability, and functionality tolerance in living radical polymerization. Multifunctional ligands are efficiently incorporated into the core of star polymers by sequential tandem procedures: 1) ruthenium-catalyzed living radical polymerization, 2) in situ core hydrogenation, and 3) core-ruthenium removal. Typically, the star polymer ligands comprising multiple phosphines and amines within the core cooperatively enclose a ruthenium complex (>100 per core). As a result, the in-core pseudo hetero P,N-chelation of the ruthenium complexes not only showed high activity for methyl methacrylate but also high tolerance to unprotected methacrylic acid.