Flash photolysis of Cu(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup 2+}-poly(acrylate) generates an intermediate, Cu{sup III}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4})-alkyl, in less than 20 ps. This intermediate decomposes into Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}) with a 20-{mu}s lifetime. We have followed, in a millisecond time scale, the disappearance of Cu(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup +}, a process that exhibits a kinetics expected for consecutive first- and second-order reactions. The reactions rates are dependent on the number of photochemically generated Cu(I) species per molecule of poly(acrylic acid) but are independent of the solutions' bulk viscosity. Flash irradiations of Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4})-poly(acrylate) complexes in aqueous solutions form metastable Cu{sup II}(ligand radical)-poly(acrylate) complexes. By contrast, Cu{sup I}(2,3,9,10-Me{sub 4}-(14)-1,3,8,10-tetraeneN{sub 4}){sup +} in methanol exhibits no photoreactivity. 17 refs., 5 figs., 3 tabs.