With the extensive use of lithium-ion batteries (LIBs), neglecting to recycle graphite anodes from LIBs leads to environmental pollution and the waste of graphite resources. Thus, developing an efficient and environment-protecting approach to reusing spent graphite anodes is necessary. Here, high value-added graphene sheets (GS), carbon nanohorns (CNHs), fluorine-doped CNHs (F-CNHs), and amorphous carbon nanoballs (ACNs) were prepared from spent graphite anodes of LIBs via DC arc plasma. In order to control the conversion of spent graphite anodes into various carbon nanomaterials, the growth mechanism of carbon nanomaterials is investigated by quenching rate. Benefiting from the extremely high quenching rates (>1.8 × 106 K/s) produced by DC arc plasma, the particle size of the prepared ACNs and CNHs is small and evenly distributed. The CNHs show a “dahlia-like” structure, and the number of graphene layers is only 3–8. Furthermore, the structural transformation mechanism of carbon nanomaterials is researched by deposition temperature. The ACNs, few-layer GS, and CNHs produced by the high quenching rates are unstable and prone to structural transformation. When these carbon nanomaterials are deposited on the cathode surface and cathode holder, the ACNs, “dahlia-like” CNHs, and GS undergo processes of fusing and overlaying at high temperatures, respectively, resulting in the agglomeration and increased particle size of ACNs and “seed-like” CNHs. Meanwhile, the GS is bent and converted into carbon nanocages (CBCs). Overall, the carbon nanomaterials prepared using spent anodes from LIBs by arc plasma are a facile, environment-friendly, and economical strategy to achieve high value-added utilization of the graphite.