AbstractA novel macrocyclic binuclear Cu(II) complex bound to poly(vinylamine) (PVAm) was synthesized by reaction of PVAm with N,N'‐trimethylene bis(3‐formyl‐5‐methylsalicylaldiminato)dicopper (2+) diperchlorate (2) in water/acetone. Polymers containing different amounts of complex repeating units were obtained by varying the amount of 2 in the reaction mixture. The polymer complexes are soluble in water and methanol. Light‐green colored films were obtained when cast from aqueous solutions. The coordination structure around the macrocyclic complex in the polymer was characterized by infrared and electronic spectroscopy. The Cu — Cu interaction of the binuclear complex on the polymer were also studied by means of ESR measurement.