Polysaccharide based graft copolymer (xanthan gum‐g‐4‐vinyl pyridine) was synthesized using potassium peroxymonosulphate/ascorbic acid redox initiator in inert atmosphere at 40°C. By studying the effect of the concentration of monomer, peroxymonosulphate (PMS), ascorbic acid (AA), xanthan gum (XOH), hydrogen ion along with effect of time and temperature on grafting characteristics: grafting ratio (%G), add on (%A), conversion (%C), efficiency (%E), homopolymer (%H), and rate of grafting (Rg), the reaction conditions for optimum grafting were determined. The optimum concentration of AA, H⁺ ion, 4‐VP for maximum grafting were found to be 10.0 × 10⁻³ mol dm⁻³, 2.5 × 10⁻² mol dm⁻³, 10.0 × 10⁻³ mol dm⁻³, respectively. Maximum %G was obtained at minimum concentration of xanthan gum i.e., at 40.0 × 10⁻² g dm⁻³ and at maximum concentration of PMS i.e., at 10.0 × 10⁻³ mol dm⁻³. The optimum temperature and time duration of reaction for maximum % of grafting were found to be 45°C and 120 min respectively. The synthesized graft copolymer was characterized by FTIR analysis. Thermogravimetric analysis showed that the xanthan gum‐g‐4‐vinyl pyridine is thermally more stable than pure gum. A probable mechanism was suggested for the graft copolymerization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009