Polyacrylonitrile (PAN)-based ultrafine fibers and carbon fibers were produced by wet-spinning, and the crystal sizes and thermal and mechanical properties of the fibers were investigated. Scanning electron microscopy revealed that the superfine fibrils in the surfaces of the PAN/polyvinyl acetate (PVA) blend fibers increased slightly with increasing PAN content before removal of the PVA. Differential scanning calorimetry indicated that the PAN and PVA in the blend fibers do not mix and, therefore, each maintains their inherent thermal characteristics. The crystal sizes of the blend fibers prepared by removing PVA with water increased at 5 wt % water. The extent of the reaction of the PAN carbon fibers, as calculated from the FT-IR spectra, is maximized at the stepwise temperature of $230^{circ}C$, and the density increased significantly above this temperature. The carbon fibers had relatively good mechanical properties, as shown by their tensile strength and modulus values of 2396 MPa and 213 GPa, respectively.