Rheological study plays a significant role in hollow fiber membrane spinning process and membrane structure regulation. In this work, the rheological behaviors of polyethersulfone (PES) spinning solutions added the polyvinylpyrrolidone (grade of PVPāK30, PVPāK60, and PVPāK90) were systematically investigated by rotational rheometry to understand how the PES membrane structure changes. Results show that PVP of variable molecular weights change the rheological properties of PES spinning solution, such as the viscosity (Ī·a), nonāNewtonian index (n), flow activation energy (EĪ·), structural viscosity index (āĪ·), storage modulus (Gā²), and loss modulus (Gā²ā²). The mixture with PVPāK30 exhibits optimal spinnability but the fingerālike membrane structure is undesirable for the hemodialysis. The rheological behaviors of PES/PVPāK60 and PES/PVPāK90 reveal that increasing shear rate and temperature are effective ways to improve the spinnability of the mixture and the membrane structure is regulated. Meanwhile, the addition of PVPāK60 or PVPāK90 at their critical concentration to the PES solution can fabricate a hollow membrane with a spongeālike structure. Combining spinnability and membrane structure, PVPāK90 is a suitable additive for the hemodialysis membrane.