The mesopore structures in polyacrylonitrile (PAN) fibers during dry-jet wet spinning process were investigated by high-resolution transmission electron microscopy (HRTEM) and image analysis utilizing the ultrathin section technique. The morphologies and dimension distribution of the mesopores in the surface and core regions of the nascent fibers and PAN fibers are presented. All fibers exhibited lamellar-like structures perpendicular to the fiber axis and the mesopores were distributed between the lamellae. For nascent fibers, the size and volume of the mesopores increased with increasing air gap and decreased with increasing drawing ratio. In addition, the widths of the mesopores were larger than their lengths. Consequently, the size and content of the mesopores in nascent fibers could be adjusted by controlling coagulation conditions. During the post-spinning process, the size and volume of the mesopores in PAN fibers decreased efficiently by hot drawing in a hot water washing bath, in hot steam chambers or on hot rollers. Moreover, the lengths of the mesopores were larger than their widths. In all fiber samples, the number and size of the mesopores in the core region were larger than those in the surface region. In addition, the mechanical properties of fibers were correlated with dimension of the mesopores. Their tensile strength increased with decreasing mesopore widths and lengths.