The viscoelastic behavior of concentrated polyacrylonitrile (PAN) /1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solutions at different concentrations and temperatures has been investigated by rheology. For concentrated polymer solutions at low temperature (40°C), the shear viscosity was found to show a raid decrease from the ending of Newtonian plateau. At relatively high shear rate or frequency for the concentrated PAN/[BMIM]Cl solutions, the deviation from the empirical Cox–Merz rule was quite evident, which suggested the formation of heterogeneous structures within these solutions. However, the dependence of G′ and G″ on angular frequency presented approximate linearity with similar slope at some temperatures between 100°C and 20°C. All the results lead us to the fact that the gelation has occurred within the concentrated solutions during cooling and the process was found to be thermoreversible. The gelation temperatures of the solutions have exhibited strong concentration dependence. It may be suggested that the microphase separation may be the major reason for the gelation of the concentrated PAN/[BMIM]Cl solutions during cooling process. POLYM. ENG. SCI., 54:598–606, 2014. © 2013 Society of Plastics Engineers