Ruthenocene-containing methacrylate homopolymer, poly(2-(methacrylolyoxy) ethyl ruthenocenecarboxylate) (PMAERu), was prepared by controlled polymerization methods such as reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Kinetic studies showed that both the RAFT and ATRP process of monomer 2-(methacryloyloxy)ethyl ruthenocenecarboxylate (MAERu) followed a controlled/"living" polymerization behavior. The obtained polymer PMAERu was fully characterized by NMR, gel permeation chromatography, UV-vis spectroscopy, cyclic voltammetry, thermogravimetric analysis, and differential scanning calorimetry. By using the ruthenocene-containing homopolymer as a Macro-RAFT agent and 2-bromoisobutyryl end-capped poly(ethylene oxide) (PEO-Br) as a macroinitiator, different amphiphilic diblock copolymers were synthesized via successful chain extension. These amphiphilic diblock copolymers can self-assemble into micelles with different morphologies, including spherical and worm-like nanostructures.