Silver nanoparticles (Ag NPs) were synthesized greenly into the lamellar space of rectorite (REC) with quaternized carboxymethyl chitosan (QCMC), meanwhile quaternized carboxymethyl chitosanirectorite/silver bionanocomposite was obtained. Results showed that QCMC and rectorite acted as reducing agent and solid support for Ag NPs, respectively. Exfoliated rectorite (REC) and organic rectorite (OREC) were obtained, simultaneously Ag NPs were formed on their interlayer and external surface. With the confinement effect of rectorite, the average diameters of Ag NPs changed from 45 nm to 22 nm, along with the change in size distributions from 30-65 nm to 18-28 nm, and their shapes changed from sphere to oval. The obtained quaternized carboxymethyl chitosan/rectorite/silver bionanocomposites were made into beads (similar to 1 mm) to catalyze the reduction of 4-nitrophenol (4-NP), the catalytic rate followed the order: the beads with OREC > those with REC > those without rectorite. The beads with quaternized carboxymethyl chitosan/rectorite/silver bionanocomposites without any treatments still performed well for four consecutive catalytic experiments. Using rectorite to stabilize Ag NPs and get smaller Ag NPs with narrower size distribution may extend the synthesis strategy of other nanoparticles. (C) 2014 Elsevier B.V. All rights reserved.