Here we report a facile strategy to synthesize porous FexCo3−xO4 nanocages by heating Prussian blue analogues FeyCo1−y[Co(CN)6]0.67nH2O nanospheres with tunable size and morphology. The iron doping amount had significant influence on the final morphology and the most uniform nanocages were obtained from x = 0.8. The catalytic performance of the nanocages was thoroughly evaluated by activation of peroxymonosulfate (PMS) for removal of bisphenol A (BPA) in water. The influence of different process parameter on the BPA degradation efficiency was examined and the catalytic stability was tested. The BPA degradation pathway was proposed based on GC–MS and LC–MS results. The involved radicals were identified through radical scavenging experiments and electron paramagnetic resonance spectroscopy. Mössbauer and XPS techniques were applied to illustrate the catalytic mechanism and B-site CoII on the surface of FexCo3−xO4 nanocages was determined as the main factor for PMS activation. Results indicate that porous FexCo3−xO4 nanocages are available to serve as alternative environmentally friendly catalysts for pollutants removal by activation of PMS.