This study presents a new type of composite consisting of piezoelectric poly(γ-benzyl-α, L-glutamate) (PBLG) polymer fibers, which contain a large dipole moment, and the elastomer polydimethylsiloxane (PDMS) as the matrix material. PBLG microfibers were fabricated and polarized using the electrospinning method and cast in PDMS to form a unidirectional continuous-fiber composite. The PBLG/PDMS composite was characterized based on various aspects such as crystalline structure, mechanical properties, piezoelectricity, and electromechanical response. The piezoelectric charge constants in the transverse and longitudinal modes were measured to be 10.2 and 54 pC/N, respectively, which are the largest piezoelectric coefficients of biocompatible polymers up to date. The thin PBLG/PDMS composite film can produce up to 200 mV peak-to-peak under sinusoidal actuation and exhibit ultra-sensitivity up to 615 mV N −1 . These results show the great potential of the highly flexible piezoelectric polymer fiber-based composite for use in a variety of applications such as energy harvesting devices, biomechanical self-powered structures, and force sensors.