A facile and green method to synthesize stable Ag nanoparticles (Ag NPs) with a narrow size distribution in water is reported. Water-soluble quaternized carboxymethyl chitosan (QCMC) with a surfactant-like structure was used as both a reducing and stabilizing agent under microwave irradiation via the modified Tollens reaction. In order to study the preparation mechanism, carboxymethyl chitosan (CMC) and quaternized chitosan (QCS) were compared as both reducing and stabilizing agents. Full characterization was performed using UV-vis, XRD, TEM, AAS, FT-IR, NMR and TGA. The results revealed that the prepared Ag NPs were mostly spherical with a small proportion being cylinders or cuboids; they were stable due to the package of the macromolecules; the diameters were 10.24 ± 3.13 nm. The Tollens reaction followed first order kinetics, and the Ea was 102.4 kJ mol(-1) for QCMC/Ag NP composite. During the growth of the Ag NPs, some quaternary ammonium groups and carboxymethyl groups were respectively oxidized to -CH2COCH3 and -CH3 groups, and the quaternary ammonium groups were more helpful for the growth of Ag NPs than the carboxymethyl groups. In addition, QCMC/Ag NP composite had much higher thermal stability than QCMC.