Fluorinated polyethylene propylene (FEP) bipolar ferroelectret films with a specifically designed concentric tunnel structure were prepared by means of rigid-template based thermoplastic molding and contact polarization. The properties of the fabricated films, including the piezoelectric response, mechanical property, and thermal stability, were characterized, and two kinds of energy harvesters based on such ferroelectret films, working in 33- and 31-modes respectively, were investigated. The results show that the FEP films exhibit significant longitudinal and radial piezoelectric activities, as well as superior thermal stability. A quasi-static piezoelectric d33 coefficient of up to 5300 pC/N was achieved for the FEP films, and a radial piezoelectric sensitivity of 40,000 pC/N was obtained in a circular film sample with a diameter of 30 mm. Such films were thermally stable at 120 °C after a reduction of 35%. Two types of vibrational energy harvesters working in 33-mode and 31-mode were subsequently designed. The results show that a power output of up to 1 mW was achieved in an energy harvester working in 33-mode at a resonance frequency of 210 Hz, referring to a seismic mass of 33.4 g and an acceleration of 1 g (g is the gravity of the earth). For a device working in 31-mode, a power output of 15 μW was obtained at a relatively low resonance frequency of 26 Hz and a light seismic mass of 1.9 g. Therefore, such concentric tunnel FEP ferroelectric films provide flexible options for designing vibrational energy harvesters working either in 33-mode or 31-mode to adapt to application environments.