Acrylic acid (AA) and acrylonitrile (AN) were used to carry out grafting on polyester (PE) fibers using the techniques of initiation by γ-radiation as well as benzoyl peroxide. The nature of the grafted fiber substance was found to be the same, irrespective of the grafting technique. Extent of grafting depended upon the time, concentration of the initiator, and the monomer as well as on the irradiation dose. The increase in the moisture regain was directly proportional to the amount of graft in the fiber. AA grafted fibers were rendered more hydrophilic than AN grafted fibers for equivalent amount of grafts. Considerable improvement in dyeability of the PE fibers was possible through grafting. About 50% to 100% improvement with disperse dyes was observed in case of PE fibers containing 22.4% and 9.0% graft of AA and AN, respectively. Intense fast dyeing with direct and basic (cationic) dyes was also possible, and the dye content was proportional to the extent of graft introduced in the fiber. The CN groups were reduced to NH2 groups in the AN graft on the fiber. In this way, deep, fast, and bright dyeing was obtained with reactive dyes. Electrokinetic studies were carried out on the grafted fibers. With the increased amount of AA graft, the maxima in the zeta potential curve shifted toward higher acidic pH as greater amounts of alkali was utilized by the COOH groups in the graft. In this respect, CN groups were less sensitive due to their lesser polarity as compared to the carboxylic groups. It was observed from surface charge density (S.C.D.) studies that the effective surface area of the fiber decreased with the increase in the amount of graft, particularly in case of AN graft. Surface conductivity (S.C.) studies revealed that with increase in the number of polar groups (COOH) on the surface of the fiber, the S.C. increased with the increase in the amount of AA graft. In case of AN grafts, the reduction in effective surface area of the fiber played a more important role than the contribution by the CN groups to surface conductivity.