The carbon anode material for lithium-ion battery was prepared by pyrolysis fuel oil and waste polyethylene terephthalate (PET) additive. The pitch was synthesized as a medium material for carbon anode by heat treatment. The waste PET additive improved the softening point and thermal stability of the pitch. La and Lc of the anode material (heat-treated pitch) increased at higher treatment temperature but decreased by waste PET additive. The electric capacity was evaluated based on effects of defective cavity and developed graphite interlayer, respectively. When the La and Lc of the anode material decreased, the electric capacity by cavity increased based on defective graphite structure. Therefore, the addition of waste PET causes the improved capacity by the cavity. The anode material which has a high efficiency (over 95%) and C-rate (95%, 2 C/0.1 C) was obtained by controlling the process of heat treatment and PET addition. The mechanism of lithium-ion insertion was discussed based on effects of defective cavity and developed graphite interlayer.