Electrospinning of polymeric solutions entails high jet velocities which could orient the polymer molecules along the jet direction. Polarized Fourier Transform IR spectroscopy (FTIR), Wide angle X-ray diffraction (WAXD) and Microelectromechanical System (MEMS)-based single nanofiber mechanical property experiments were employed to investigate the molecular orientation and crystallinity in electrospun polyacrylonitrile (PAN) nanofibers produced under different electrospinning conditions with diameters mainly varying between 100 and 300 nm. FTIR measurements with nanofibers fabricated at three different electrospinning distances, but under the same electric field intensity, revealed an enhanced molecular orientation only for the longest electrospinning distance. At long electrospinning distances the fiber solvent content is substantially reduced resulting in high viscosity, and, therefore, sustained shear stresses, which, in turn, allows for permanent molecular orientation. The orientation factors from polarized FTIR were in good agreement with the mechanical property trends obtained from individual nanofibers, where high elastic moduli and yield strengths were recorded from nanofibers with diameters smaller than 300 nm, which were fabricated at the longest electrospinning distance. WAXD studies on bundles of aligned PAN nanofibers showed small crystallinity which did not follow the trends in the mechanical properties and varied rather non-monotonically from 7%, for fibers spun at the shortest distance, to 17% for fibers spun at the longest distance used in this study. (C) 2011 Elsevier Ltd. All rights reserved.