Electrochemical and spectroelectrochemical studies were conducted on thin films of poly- tris(4-vinyl-4 ' -methyl-2,2 ' -bipyridine)ruthenium(II) which were formed by electrochemical reductive-polymerization. These homopolymer films undergo a process whereby redox charge is trapped in the film when the potential is scanned between the formal Ru(I/II) and Ru(II/III) couples of the polymer. This trapped charge is then released at the leading edge of each respective bulk redox process. The results of these studies show that the redox sites responsible for this trapped charge have potentials that lie exclusively in die potential region between the two bulk processes. Additionally, difference spectra obtained during the charge-release indicate that the oxidative and reductive processes have important qualitative and quantitative differences.