We present the synthesis of ring-opening metathesis polymerization block polymers containing a ruthenium bipyridine luminescent block and a hydrophobic block and end-terminated with a biologically active biotin molecule. These copolymers undergo self-assembly in water into star micelles containing a large number of luminescent Ru(II) centers, with the hydrophobic block in their core and the molecular recognition unit biotin at their periphery. Addition of the protein streptavidin results in the cross-linking of these polymer nanospheres, through biotin-steptavidin binding, into extended networks. In addition to its usefulness as a method to organize polymeric nanostructures into biochemically addressable networks, this study has generated luminescent micellar aggregates capable of binding to biological compounds, and thus useful for the luminescence detection and signal amplification of biomolecules.