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The concentrated polyacrylonitrile (PAN) solutions were prepared with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as solvent by static state, stirring, and kneading. The steady and oscillatory shear tests were carried out to investigate the viscoelastic behaviors of the PAN/[BMIM]Cl solutions by rotational rheometer. It was found that the zero shear-rate viscosity and relaxation time of the solution prepared by kneading were lowest and the non-Newtonian index was largest among the solution. During kneading, the gelation temperature of the viscous and homogenous solution was at the lowest temperature 22.7°C among the all three solutions. Only the solutions prepared by stirring and kneading could be spun by dry-jet wet spinning technology. The fiber processed with the solution prepared by kneading could be drawn with a higher draw ratio, showing the larger draw ability. The supramolecular structure and properties of the fibers were studied by synchrotron wide-angle X-ray diffraction (WAXD) technologies, dynamic mechanical analysis (DMA), and mechanical tests. All the results showed that the kneading is an efficient method for PAN fiber spinning with [BMIM]Cl as solvent. It lead to the investigation of the methods of preparation of PAN solution in [BMIM]Cl, which affect the homogeneity of the solutions and hence the resulting characteristics of PAN fibers. POLYM. ENG. SCI., 55:558–564, 2015. © 2014 Society of Plastics Engineers