The development of alternative anode materials out of flexible composite nanofibers has seen a growing interest. In this paper, binary carbon nanofiber electrodes of SnO2/NiO and Sn nanoparticles are produced using a scalable technique, Forcespinning (FS), and subsequent thermal treatment (carbonization). The Sn/C composite nanofibers were porous and flexible, while the SnO2/NiO composite nanofibers had “hairy-like” particles and pores on the fiber strands. The nanofiber preparation process involved the FS of Sn/PAN and SnO2/NiO/PAN solution precursors into nanofibers and subsequent stabilization in air at 280 °C and calcination at 800°C under an inert atmosphere. The flexible composite nanofibers were directly used as working electrodes in lithium-ion batteries without a current collector, conducting additives, or binder. The electrochemical performance of the SnO2/NiO/C and Sn/C composite fiber anodes showed a comparable cycle performance of about 675 mAhg−1 after 100 cycles. However, the SnO2/NiO/C electrode exhibited a better rate performance than the Sn/C composite anode and was able to recover its capacity after charging with a higher current density. A postmortem analysis of the composite nanofiber electrode after the aging process revealed a heavily passivated electrode from the electrolyte decomposition by-products. The synthesis and processing methods used to produce these composite nanofibers clearly were a factor for the high rate capability and excellent cycle performance of these binary composite electrodes, largely on the account of the unique structure and properties of the composite nanofibers.