The photochemical and photophysical properties of the polymers {(vpy-CH3+)(2)-vpyRe(CO)(3)(phen)(+)}(200) (vpy = vinyl pyridine, phen = 1,10-phenanthroline) have been investigated in solution phase and compared to those of a related polymer, {(vpy)(2)-vpyRe(CO)(3)(phen)(+)}(200), and monomer, pyRe(CO)(3)(phen)(+). Irradiations at 350 nm induce intrastrand charge separation in the peralkylated polymer, a process that stands in contrast with the energy migration observed with {(vpy)(2)-vpyRe(CO)(3)(phen)(+)}(200). Electronically excited -vpyRe(CO)(3)(phen)(+) chromophores and charge-separated intermediates react with neutral species, e.g., 2,2',2"-nitrilotriethanol, and anionic electron donors, e.g., SO32- and 1(-). The anionic electron donors react more efficiently with the metal-to-ligand charge transfer excited state of these polyelectrolytes than with the excited state of pyRe(CO)(3)(phen)(+).