Electrospun poly(vinylidene fluoride) (PVDF) nanofibers were collected on aluminum foil across a gap with widths that varied in size from 2 to 10 mm. Scanning electron microscopy (SEM) images on fiber bundles showed that in all cases, fibers in the gap were macroscopically aligned across the gap. However, single fiber selected area electron diffraction (SAED) patterns and polarized Fourier Transform Infrared (FTIR) spectra demonstrated that fibers deposited across the gap were also highly aligned at the molecular level with the polymer backbones oriented along the fiber axis and that the extent of molecular orientation increased with the gap width. A possible explanation for this observation is based on the repulsion of similarly charged nanofibers and the simultaneous attraction of these fibers to the oppositely charged gap edges. This provides a plausible model for understanding the deposition kinetics and subsequent molecular orientation as a function of gap size when electrospinning using this method of fiber collection. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 617-623