Binder-free, highly porous carbon nanofibers (CNFs) with novel sponge-like pore structures were synthesized for the first time via centrifugal spinning of cellulose-based polymers, and SnO2 was introduced to improve the electrochemical performance. Cellulose-based binder-free centrifugally spun carbon-coated SnO2/carbon nanofibers (C@SnO2/CNFs) were employed as anodes in Na-ion batteries. Owing to their highly porous morphology with novel sponge-like pore structures and SnO2 nanoparticles providing rapid Na-ion transport, better electrolyte accessibility, and good mechanical strength, the C@SnO2/CNFs showed outstanding electrochemical performance, with a high reversible capacity of 660 mAh/g at 50 mA/g, high rate capability, and excellent cycling performance. The specific capacity of C@SnO2/CNFs was approximately 390 mAh/g after 2000 cycles at 0.2 A/g. These results prove that the combination of centrifugal spinning, carbon coating, and heat treatment is a promising and sustainable approach for creating cellulose-based carbon nanostructures with highly porous structures that can be used to synthesize high-performance electrodes for energy storage systems.