The anionic graft copolymerization of E-caprolactam onto a Kevlar-49 fiber surface was carried out by using a metalation reaction in a dimethyl sulfoxide solution of sodium hydride. The effects of reaction conditions on the graft yield and on the tensile strength of the fiber have been investigated. Graft yield significantly increased with increasing metalation time, NaH concentration, and monomer concentration. The graft yield varied from 6 to 32% with reaction conditions. The tensile strength of the fiber depended predominantly on NaH concentration. The retained tensile strength was over 93% when the concentration of NaH was below 2.1 mmol/L per 0.5 g of Kevlar. The discontinuous Kevlar fiber reinforced composites were prepared by a blending/ melt-pressing method. In thermomechanical and dynamic mechanical analyses, the relaxation peak of grafted Kevlar fiber/Nylon 6 composite film moved to higher temperatures, compared with the original Kevlar fiber/Nylon 6 composite film. The grafted Kevlar fiber reinforced Nylon 6 composite film exhibited mechanical properties superior to those of the original Kevlar fiber reinforced composite film. The higher thermal and mechanical properties were due to the effect of higher interfacial interaction between the grafted Kevlar fiber and matrix.