Poly 4( 5) vinylimidazole (PVIm) and a series of copolymers of 4 - vinylpyridine and melhylmelhacrylate (PVP-MMA) were prepared and reacted with hydrated bis(2.2'-bipyridyl)ru1henium dichloride IRu(bpy) 2- CI2 .2 H 201. The mole ratio of 4-vinylpyridine units to melhylmelhacrylate (4VP:MMA) was varied belween 1 :5 to 6:1 and the mole ratio of 4VP to ruthenium <4VP:Ru) varied between 1.15:1 to 106:1. In this work the spectroscopic and electrochemical properties of the melallopolymers thus formed bolh as coalings on electrode surfaces and in solution are described. It is shown Ihat depending on Ihe reaction conditions and 1he polymer backbone, different types of ruthenium-polymer complexes are formed. The spectroscopic and electrochemical properties of Ihe rulhenium-(PVIm) melallopolymers are compared to those of mononuclear 4-melhylimidazole compounds of Ru(bpy) 2. Chronocoulomelry was used to obtain an indication of the ease of charge transport across a film of metallopolymer attached to a glassy carbon electrode. It was found that as the amount of MMA in the copolymer backbone increases, the activation energy for charge transport (E a) increases and hence charge transport becomes more difficult. The values of Ea obtained both for the (P V P - MMA) and (PVIm) metallopolymers suggest that some movement of the polymer chains is necessary for charge transport. Electrodes modified with these metallopolymers were found to mediate the oxidation of Fe11 in solution at potentials were the ruthenium-polymer complex was reduced. As the amount of MMA in the copolymer backbone increased, it was found that the mediation became less efficient. The results for the photolysis of these metallopolymers in various solvents and as thin films on electrodes are similar to those obtained for Ru( bpy) 2- ( poly 4-vinylpyridine or poly N - vinylimidazole).