Electrospinning is the only known technique for fabrication of long non-woven ultrafine-fibers. However, a number of limitations, including low productivity and clogging of a spinneret, substantially paralyses industrial scale up of the process. Clogging is indeed an unavoidable phenomenon during electrospinning of biopolymers and the exact reason for clogging is still unclear. The aim of the present study was thus to investigate the clogging phenomenon via the study of a solution of zein/ethanol, which was used as a model biopolymer system. The gel-like substance causing clogging at the spinneret was collected and its infrared spectrum and rheological properties were determined via Fourier transform infrared (FTIR) spectrophotometry and rheometry, respectively. The results indicated that clogging was due to solvent evaporation, which led to formation of a highly viscous semi-solid at the spinneret. Moreover, the results also revealed that the applied voltage and polymer concentration were the key parameters affecting clogging. A means to help avoid clogging and hence an ability to continuously perform electrospinning was also proposed and tested. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 1821 1829, 2010