Ultra-high molecular weight polyacrylonitrile (UHMW-PAN ) was prepared by aqueous suspension polymerization, and the effect of molecular weight on its rheological behaviors hi dimethylsulf oxide (DMSO) and the spinning stability were investigated. It shows that, compared with common polyacrylonitrile ( C-PAN), UHMW-PAN/DMSO solution has smaller non-Newtonian index, larger structural viscosity index, much longer maximum relaxation time, and no first-Newtonian region appears in the flow curves under the same experimental conditions. The explanations for these phenomena are given in the view of chain-entanglements. The optimal technology of preparing UHMW-PAN fibers and hollow fiber membranes could be obtained based on the rheological study. Ultra-high molecular weight polyacrylonitrile (UHMW-PAN) was prepared by aqueous suspension polymerization, and the effect of molecular weight on its rheological behaviors hi dimethylsulfoxide (DMSO) and the spinning stability were investigated. It shows that, compared with common polyacrylonitrile C-PAN), UHMW-PAN / DMSO solution has smaller non-Newtonian index, larger structural viscosity index, much longer maximum relaxation time, and no first-Newtonian region appears in the flow curves under the same experimental conditions. The explanations for these phenomena are given in the view of chain-entanglements. The optimal technology of preparing UHMW-PAN fibers and hollow fiber membranes could be based on the rheological study.