The postdrawing process is poorly understood for polymer nanofibers due to the difficulty of manipulating nanofiber structures. Here, an angled track system facilitates postdrawing of individual nanofibers with control of parameters including molecular weight, draw rate, draw ratio, and solvent evaporation time. In this study, the effects of molecular weight, draw rate, and relative residual solvent content on final nanofiber properties are investigated. Molecular weight is first investigated to clarify any influence polymer chain length can have on drawing in facilitating or hindering chain extensibility. Polyacrylonitrile nanofibers with 50 and 150 kDa molecular weights behave similarly with postdrawing resulting in reduced diameters and enhanced mechanics. Since solvent quantity during drawing is a time sensitive component it is meaningful to assess the impact of draw rate on the chemical and structural makeup of postdrawn fibers. Chemical bond vibrations and chain orientation are sensitive to draw rate when polycaprolactone nanofibers are dried for 3 minutes prior to postdrawing, but this dependency to draw rate is not observed when fibers are postdrawn immediately upon collection. These findings demonstrate that the amount of retained solvent at collection is relevant to this postprocessing approach, and highlights the dynamics of solvent evaporation during postdrawing.