Electrospun poly(L-lactic acid) (PLLA) nanofiber web based sensors were studied for their shear-piezoelectric behavior as a function of varying nanoweb stacking arrangement (constructive, destructive and multi-layered folding) as well as electrode architectures (series and parallel). Initial data obtained from ATR-IR spectra confirmed the effect of electrospinning on the dipole and chain orientations in PLA nanofiber web compared to its thick film. After optimization of the sensor fabrication conditions using ATR-IR and piezoelectric output signal data, the best performing PLA nanofiber web based sensor (folded nanofiber web with parallel connection of electrodes) was also demonstrated to work as a power source to charge a capacitor as well as to operate LEDs, which signifies the great potential of the present study for many commercial applications. (C) 2015 Elsevier B.V. All rights reserved.