Waste-activated sludge (WAS) disintegration using peroxydisulfate (PDS) has attracted scientific attention over the past few years. Despite several advantages offered by a sulfate radical-advanced oxidation process, there are still too many downsides of this treatment that limit its facile large-scale application. This study investigated whether modifying nano zero-valent iron (nZVI) with a second metal such as Ag and Cu enhanced the disruption of WAS. The disintegration efficiency was assessed using standard techniques, i.e., soluble chemical oxygen demand, Fourier-transform infrared spectroscopy and a scanning electron microscope. The bimetallics were shown to have an improved disintegration efficiency of > 2.5-fold compared with the untreated sample. Furthermore, nZVI/Ag was found to be more efficient than nZVI/Cu for PDS activation, which was validated by the higher ratio (3 and 2.5 for nZVI/Ag and nZVI/Cu, respectively) between the soluble extracellular polymeric substances and the bound extracellular polymeric substances (S-EPS/B-EPS). Similar conclusions were derived from a SEM analysis. The improved disintegration efficiency could be related to the enhanced electron transfer from nZVI to PDS or the intrinsic properties of silver, which was found to be one of the best activators for PDS under homogeneous conditions. We believe that this study deepens the understanding of PDS heterogeneous activation processes.