This research considers the effect of added mesophase pitch (MP) as an additive during the pitch synthesis reaction of pyrolyzed fuel oil (PFO). Two effects are generated by adding MP. One is an enhancement of thermal stability due to the high thermal property of the additive; the other is that the volatile compounds that were removed by vaporization of PFO during the thermal reaction can participate in the pitch synthesis reaction (PFO→pitch) more efficiently. The effect differs according to the amount of the additive. When the amount of the additive is less than 7 wt%, the first effect is dominant, whereas the second effect is dominant when the additive amount exceeds 10 wt%.