Two types of hard carbon materials were synthesized through direct pyrolysis of commercial polyvinyl chloride (PVC) particles and pyrolysis of PVC nanofibers at 600-800 degrees C, respectively, where the nanofibers were prepared by an electrospinning PVC precursors method. These as-prepared hard carbon samples were used as anode materials for Na-ion batteries. The hard carbon obtained from PVC nanofibers achieved a high reversible capacity of 271 mAh/g and an initial Coulombic efficiency of 69.9%, which were much superior to the one from commercial PVC, namely, a reversible capacity of 206 mAh/g and an initial Coulombic efficiency of 60.9%. In addition, the hard carbon originated from the PVC nanofibers exhibited good cycling stability and rate performance: the initial discharge capacities were 389, 228, 194, 178, 147 mAh/g at the current density of 12, 24, 60, 120, and 240 mA/g, respectively, retaining 211 mAh/g after 150 cycles. Such excellent cycle performance, high reversible capacity, and good rate capability enabled this hard carbon to be a promising candidate as anode material for Na-ion battery application.