Herein we report a new, simple, low cost and one step way to obtain silica-supported silver nanoparticles (AgNPs) on commercial polyethyleneimine-functionalized silica beads (SiO2-PEI) under mild experimental conditions. The novel AgNPs/(SiO2-PEI) material has been thoroughly analyzed using FE-SEM, BET, XRD, XPS and XE-AES analysis. The reduction of Methylene Blue (MB) to Leuco Methylene Blue (LMB) in the presence of NaBH4 was chosen for testing the catalytic properties of AgNPs/(SiO2-PEI) towards dyes decoloration. Moreover, the prepared supported nanocatalyst was also found to exhibit excellent catalytic activity towards decoloration of some azo dyes such as E110 and E122.