We report excellent piezoelectric and pyroelectric properties of electrospun nanofibers based on the hybrid ferroelectric 1,4-diazabicyclo[2.2.2]octane perrhenate (dabcoHReO4). Ferroelectric nanoparticles are embedded into the fibers being naturally aligned with the major polarization component along the fiber axis. A flexible piezoelectric nanogenerator consisting of an aligned array of dabcoHReO4 fibers provides a voltage above 100 mV under a moderate strain level. The pyroelectric coefficient in as-electrospun dabcoHReO4 fiber mat is similar to that in poled polyvinylidene difluoride nanofibers. The results show that the nanofibers based on dabcoHReO4 have a great potential for pyroelectric and piezoelectric autonomous energy harvesting with natural advantages such as biocompatibility, flexibility, low cost, and easy fabrication.