AbstractFor the study of the effect of ceric ammonium nitrate (CAN) initial concentration on the graft copolymerization of 4‐vinylpyridine (4‐VP) onto cotton three series of experiments were carried out. In the first one the CAN concentration was varied from 0.5 to 100 mmol/l and so, parallely, the total nitrate ion concentration. In the other two series the CAN initial concentration was varied, but keeping the total nitrate ion concentration constant at 1.09 and 1.59 M, respectively, by sodium nitrate addition. Increasing the ceric salt concentration the graft yield and total conversion reached a maximum. When the nitrate ion concentration was kept constant the maximum graft yield value was achieved at CAN concentrations lower than when it was varied. However, for all the three series of experiments the maximum graft yield value was nearly the same. The ceric ion consumption increased with increasing initiator concentration. The higher the total nitrate ion concentration, the higher was the ceric ion consumpt