FexMnyCuzOw/γ-Al2O3 nanoparticles were prepared by a wet impregnation -calcination method and characterizedby means of XRD, BET, SEM-EDS. Box-Behnken design was used to investigate the degradation of PVA in aqueoussolution. Besides, the effect of different calcination temperature, FexMnyCuzOw/γ-Al2O3 dosage, H2O2 dosage, initial PVAconcentration and initial solution pH on the removal of PVA were also studied. Results showed that PVA can be efficientlyremoved and oxidized by the heterogeneous Fenton-like process with appropriate amount of FexMnyCuzOw/γ-Al2O3 andH2O2. In this paper, the efficiency of PVA was above 90 % by FexMnyCuzOw/γ-Al2O3 nanoparticles at an initial PVAconcentration below 25 g/l, temperature at 60 oC, initial pH from 1.0 to 6.0, H2O2 and catalyst dose of 60 ml/l and 0.5 g/l,respectively. In addition, chromatography (GPC) was applied to further analyze the degradation of PVA under differentexperimental conditions, which revealed that the backbone chain of PVA could be effectively broken and oxidized. Severalunsaturated degradation products, including butanones, benzaldehydes, hexanals and acetic acids were also detected andidentified by gas chromatography-mass spectrometry (GC-MS). Besides, the nano catalyst maintained favorable catalyticability during the five-times utilization, which means it could be recycled by filtration and calcination.