The accurate prediction and manipulation of nanoscale product sizes is a major challenge in material processing. In this investigation, two process characteristics were explored during the modified coaxial electrospinning of zein, with the aim of understanding how this impacts the products formed. The characteristics studied were the spreading angle at the unstable region (θ) and the length of the straight fluid jet (L). An electrospinnable zein core solution was prepared and processed with a sheath comprising ethanolic solutions of LiCl. The width of the zein nanoribbons formed (W) was found to be more closely correlated with the spreading angle and straight fluid jet length than with the experimental parameters (the electrolyte concentrations and conductivity of the shell fluids). Linear equations W = 546.44L - 666.04 and W = 2255.3θ - 22.7 could be developed with correlation coefficients of Rwl2 = 0.9845 and Rwθ2 = 0.9924, respectively. These highly linear relationships reveal that the process characteristics can be very useful tools for both predicting the quality of the electrospun products, and manipulating their sizes for functional applications. This arises because any changes in the experimental parameters would have an influence on both the process characteristics and the solid products' properties.