Electrospun nanofiber mats containing carbon nanoparticles in a poly(vinylidene fluoride) binder were prepared and characterized as Li-ion battery anodes. The mats exhibited an initial capacity of 161mAhg(-1) with 91.7% capacity retention after 510cycles at 0.1C (1C=372mAg(carbon)(-1)). Whereas many nanoscale electrodes are limited to low areal and/or volumetric capacities, the particle/polymer nanofiber anodes can be made thick with a high fiber volume fraction while maintaining good rate capabilities. Thus, a nanofiber anode with a fiber volume fraction of 0.79 exhibits a volumetric capacity of 55mAhcm(-3) at 2C, which is twice that of a typical graphite anode. Similarly, thick nanofiber mats with a high areal capacity of 4.3mAhcm(-2) were prepared and characterized. The excellent performance of electrospun anodes is attributed to electrolyte intrusion throughout the interfiber void space and efficient Li+ transport between the electrolyte and carbon nanoparticles in the radial fiber direction.