The presence of silver nanoparticles (AgNPs) in water bodies has emerged as a new environmental concern and the efficient separation of these nanoparticles remains a critical challenge. Here, we developed novel magnetic nanoflocculants for the recovery of AgNPs from water. Alternating layers of biopolymers, in particular, chitosan, alginate, and polymeric bio-based soluble substances (BBS) derived from urban waste, were coated on magnetic nanoparticles via the layer-by-layer technique to prepare reusable magnetic nanoflocculants (MNFs). The MNFs obtained were characterized with diverse physicochemical techniques. Surface response methodology, based on the Doehlert matrix, has shown to be a useful tool to determine the effect of pH (in the range 5-9), concentration of AgNPs (7-20 mg L