Raman spectra of as-spun fibers produced through electrospinning have shown that high S/N data can be obtained on 50-mum diameter fibers in relatively short collection times (25 s). Using this same instrumental approach, "real time" Raman spectra of the electrospinning liquid fiber jet at the origin or the jet and 1 cm downstream have been obtained. The results show that "on-line" analysis of the solvent/polymer ratio and spectroscopic measurements of polymer orientation are possible and will lead to a more quantitative understanding of the development of the polymer microstructure during the electrospinning process.