Piezoelectric structures, in forms that allow mere in-surface deformations under large strains, are attractive for bio-integrated systems. Here, mechano-electrospinning (MES) is presented to direct-write straight nanofibers of polyvinylidene fluoride onto a prestrained poly(dimethylsiloxane) (PDMS) substrate, to position and polarize a piezoelectric nanofiber array in one-step. Wrinkled/non-wrinkled buckling modes are found when the substrates are released, and the morphology of the direct-written fiber proved the key to determine the buckling modes, which can be tuned precisely by MES parameters. The non-wrinkled, stretchable piezoelectric devices with a highly synchronized serpentine fiber array exhibit their in-surface deformation and stable piezoelectric performance up the failure strain of PDMS (∼110% in our study), which may be used as stretchable sensors and energy converters/providers.