Abstract By XRD/FTIR/TEM/UV–vis analysis, the existence form of bimetallic nanocomposites in alumina aerogel matrixes using the novel synthesis method were investigated. The results confirmed that the bimetallic catalyst was more active than any monometallic catalysts. The higher performance was explained in terms of a synergic association between bimetallic ions, which was further confirmed by XPS, H2-TPR. The possible reaction mechanism of bimetallic catalyst in the peroxymonosulfate (PMS) system was also given. The analysis of the oxide surface by confocal Raman and Electron paramagnetic resonance (EPR) and radical competitive reactions during the catalytic process suggested that sulfate radical and hydroxyl radical were the main radical species responsible for the organic pollutant elimination. As a green catalyst, bimetallic catalyst we prepared showed excellent recovery and stability in the repeated batch experiment.