AbstractThe contradiction between sufficient removal of middle molecular toxins and the retention of beneficial proteins is a great challenge for hemodialysis. The tree‐like structure was introduced to prepare a tree‐like PA6/PVP/CS nanofibrous membrane, which has good performance in the effective removal of middle molecular toxins and retention of beneficial proteins. The removal rates of urea and lysozyme were 75.4% and 46.3%, respectively, and the retention rate of bovine serum albumin (BSA) was 90.3%, which were 9%, 13%, and 18% higher than that of the membrane without tree‐like structure. In addition, to explore the possibility of further optimization of the tree‐like hemodialysis membrane, AC was added to prepare a tree‐like PA6/PVP/CS@AC nanofibrous membrane, which the urea removal rate was increased to 83.9%. The introduction of a tree‐like structure provides an effective way to solve the problem of protein loss and has great application potential in hemodialysis.