In order to enhance the antibacterial activity of chitosan and expand its application field, silver nanoparticles are introduced into the matrix, and the grafting modification is carried out. Chitosan grafted vanillin (CS-g-VA) is prepared with microwave-radiation method, and silver nitrate is reduced by vanillin, so that silver nanoparticles are separated evenly in CS-g-VA sol, which is Ag/CS-g-VA composite sol. The effects on the preparation of Ag/CS-g-VA composite sol are studied, and the structure and thermal property of the obtained composite sol are characterized by SEM, TEM, FTIR, XRD, UV-vis and TG-DSC. The experiment results show that the optimum conditions for the preparation of Ag/CS-g-VA are as following: Vanillin concentration of 6.0%, CS-g-VA concentration of 4.0%, and silver nitrate concentration of 0.20 mol/L. The inhibition of Ag/CS-g-VA composite sol against Escherichia coli and Bacillus subtilis is investigated through antibacterial tests. The results show that the antibacterial activity of Ag/CS-g-VA composite sol is more efficient than that of single CS materials.