This book describes the synthesis, photophysical and photochemical properties of inorganic polymers containing-Re(CO)3L+ pendants. Marked differences were found between the photochemical and photophysical properties of the polymers and those of the related monomeric complexes, pyRe(CO)3L+ (py = pyridine). The main cause of these differences is the photogeneration of the metal-to-ligand charge transfer (MLCT) excited sates in concentrations that are much larger when -Re(CO)3 L+ chromophores are bound to (vpy)n~600.