The facile production of high-purity mesophase pitch has been a long-standing desire in various carbon industries. Recently, polymer additives for mesophase production have attracted much attention because of their convenience and efficiency. We propose polyvinylidene fluoride (PVDF) as a strong candidate as an effective additive for mesophase production. The mesophase content and structural, chemical, and thermal properties of pitches obtained with different amounts of added PVDF are discussed. The influence of PVDF decomposition on mesophase formation is also discussed. We believe that this work provides an effective option for mesophase pitch production.