Electrospun nanofibers are fabricated from poly(DL-lactic acid) (PLA), and the piezoelectric-like response and waveguiding properties of these nanofibers are demonstrated. A sheet composed of randomly orientated PLA fibers sandwiched between electrodes exhibits a linear increase in thickness with increasing applied voltage. This indicates that the fibers act like a piezoelectric material. The waveguiding properties of the fibers when doped with an organic dye are investigated by aligning the fibers unilaterally. Photoluminescence from the dye propagates within the fibers, with an attenuation of <44 dB cm−1 at 590–670 nm.