Poly(ethersulfone) (PES) is one of the polymers most widely used for the fabrication of ultrafiltration or nanofiltration membranes in various applications, but its membrane suffers from fouling. In this study, preparation, characterization, and performance of PES nanocomposite membrane comprising peroxopolyoxometalate nanoparticles was studied to provide improved permeability and anti-fouling properties. The high oxygen ratio of the PW4 nanoparticles could enhance the hydrophilicity of the membranes. The PW4 nanoparticles were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and X-ray diffraction analyses. The mixed matrix membranes were fabricated using a non-solvent induced phase-separation method. The fabricated membranes were characterized using atomic force microscopy, attenuated total reflection, SEM, EDX mapping, total average porosity, thermogravimetric analyze, and water contact angle experiments. The dye flux and rejection, pure water permeability and anti-fouling properties of the membranes were investigated. All of the membranes blended by different contents of the PW4 nanoparticles presented better performance compared to the unmodified membrane. The filtration performance of the membranes in reactive green 19 (RG19) and reactive yellow 160 (RY160) dye separation showed that all of the PW4 blended membranes possessed dye rejection greater than 86% and 96% for RY160 and RG19, respectively. The reusability test using bovine serum albumin (BSA) protein and RG19 dye solutions in five cycle experiments presented good reproductivity of the PW4 blended membranes. The PES membrane containing 1 wt% of PW4 nanoparticles showed the highest flux recovery ratio (75%) as well as reduced irreversible fouling ratio (8%) through BSA protein filtration.