Nanostructures of polyvinyledenedifluoride-tetrafluoroethylene (PVDF-TrFE), a semicrystalline polymer with high piezoelectricity, results in significant enhancement of crystallinity and better device performance as sensors, actuators, and energy harvesters. Using electrospinning of PVDF to manufacture nanofibers, we demonstrate a new method to pattern high-density, highly aligned nanofibers. To further boost the charge transfer from such a bundle of nanofibers, we fabricated novel core-shell structures. Finally, we developed pressure sensors utilizing these fiber structures for endovascular applications. The sensors were tested in vitro under simulated physiological conditions. We observed significant improvements using core-shell electrospun fibers (4.5 times gain in signal intensity, 4000 μV/mmHg sensitivity) over PVDF nanofibers (280 μV/mmHg). The preliminary results showed that core-shell fiber-based devices exhibit nearly 40-fold higher sensitivity, compared to the thin-film structures demonstrated earlier.