Polyethersulfone (PES) is widely used as biomaterials due to its thermal stability, mechanical strength, and chemical inertness. Nevertheless, their blood compatibility is still not adequate for hemodialysis. Moreover, it is very difficult to change the molecular structure by chemical modification due to the very stable chemical characteristics. In this study, polyvinylpyrrolidone (PVP) was used as an additive in the preparing of PES membrane in order to improve the hydrophilicity and blood compatibility. The result shows that the PVP-added PES membrane has higher water flux, water adsorption, and lower water contact angle (CA) than the pristine PES membrane. This indicates that the hydrophilicity of PES membrane was improved through adding PVP. Moreover, adding PVP as an additive could effectively reduce bovine serum albumin adsorption and prolong the blood coagulation time, thereby improving blood compatibility of PES membrane.