In the U.S., there are over 4 million miles (6 million km) of roadways and more than 250 million registered vehicles. The energy lost in the pavement system due to traffic-induced vibration and deformation is enormous. If effectively harvested, such energy can serve as an alternative sustainable energy source that can be easily integrated to the transportation system. The potential of PVDF, which is a piezoelectric polymer material, is investigated as a potential energy harvester integrated in pavement systems. The uniqueness of this study lies in that the electrical response of PVDF under coupled mechanical and thermal stimulations are studied. It is well known that most piezoelectric materials are also pyroelectric materials, which convert temperature change into electricity. However, the potential of PVDF as a hybrid piezo-pyroelectric energy harvester has been seldom studied. Through series of well controlled experiments, it is found that there exists interesting coupling phenomenon between piezoelectric and pyroelectric effects of PVDF: the voltage generated by simultaneous mechanical and thermal stimulations is the sum of voltages generated by separate stimulations. In addition, an estimation of power generation through piezoelectric and pyroelectric effect is conducted. Finally, the overall effects of temperature on hybrid piezo-pyroelectric energy harvesting are discussed.