Mechanical properties of polyimide (PI) electrospun nanofibers could be improved by increasing imidization temperatures. However, the intrinsic mechanism on this phenomenon is highly required, which is helpful to improve mechanical properties of electrospun nanofibers by external thermal treatment. In this work, single electrospun PI nanofibers (SNF-PI) with different imidization temperatures were prepared. The nanofiber morphology was studied by SEM and AFM and the mechanical properties were measured by single fiber micro-tensile test. Polarized Raman Spectroscopy was applied to determine the PI molecular orientation in SNF-PI. The molecular orientation factor provides directly explanation on the effect of imidization temperatures on the mechanical properties of SNF-PI. (C) 2018 Elsevier B.V. All rights reserved.