A novel extensional rheometer developed at W.Virginia University was used to characterize the stretching behavior of various low viscosity model solutions (comparable to water) through the Trouton viscosity. The jetting behavior of these systems was determined using a custom-designed drop-on-demand apparatus and a camera. Key aspects of the process - tailing, ease-of-separation and satellite drop formation - were related to the extensional viscosity and enabled definition of the optimal processing window. The observed behavior was shown to be consistent with a simple mechanistic explanation in terms of a balance between the ease of drop formation and suppression of the Rayleigh instability phenomenon. This work – believed to be the first of its kind - provides a basis for efficient commercialization of this technology and future theoretical analysis.