PVDF was prepared by compression molding, and its phase content/structure was assessed by WAXD, DSC, and FTIR-ATR spectroscopy. Next, PVDF samples were aged in bioethanol fuel at 60 °C or annealed in the same temperature by 30 ─ 180 days. Then, the influence of aging/annealing on thermal stability, thermal degradation kinetics, and lifetime of the PVDF was investigated by thermogravimetric analysis (TGA/DTG), as well as the structure was again examined. The crystallinity of ~41% (from WAXD) or ~49% (from DSC) were identified for unaged PVDF, without significant changes after aging or annealing. This PVDF presented not only one phase, but a mixture of α-, β- and γ-phases, α- and β-phases with more highlighted vibrational bands. Thermal degradation kinetics was evaluated using the non-isothermal Ozawa-Flynn-Wall method. The activation energy (E a ) of thermal degradation was calculated for conversion levels of α = 5 ─ 50% at constant heating rates (5, 10, 20, and 40 °C min─1), α = 10% was fixed for lifetime estimation. The results indicated that temperature alone does not affect the material, but its combination with bioethanol reduced the onset temperature and E a of primary thermal degradation. Additionally, the material lifetime decreased until about five decades (T f = 25 °C and 90 days of exposition) due to the fluid effect after aging. © 2020 The Authors.