In the present case, the functionalization of sodium salt of partially carboxymethylated tamarind kernel powder (Na-PCMTKP, DS= 0.15), an industrially important natural polymer, is carried out through photo-graft copolymerization of methyl methacrylate (MMA) and ethyl methacrylate (EMA) onto it using ceric ammonium nitrate (CAN) as a photo-initiator. The effects of the concentrations of photo-initiator (CAN), nitric acid, methacrylate monomers (MMA and EMA) and the amount of Na-PCMTKP as well as reaction time and temperature on photo-graft copolymerization are being investigated to achieve the maximum graft yields (%G = 232.2 and %GE = 91.0 in the case of MMA and %G = 206.2 and %GE = 90.0 in the case of EMA). A suitable mechanism to explain the photo-graft copolymerization is being proposed. The kinetics aspect of the photo-graft copolymerization is also studied and the values of the overall activation energy for the photo-graft copolymerization in the case of MMA and EMA are found to be 8.10 and 10.49 kJ mol −1 , respectively. Besides kinetics study, the chemical structure and thermal properties of the graft copolymers of Na-PCMTKP containing PMMA and PEMA is studied by FTIR, TGA, and SEM techniques and the results ascertains the evidence of the successful photo-graft copolymerization of both the methacrylate monomers onto Na-PCMTKP. The synthesized novel graft copolymers may find their potential applications to be used as metal adsorbents as well as novel excipients for direct compression matrix tablets.