Characterizing the parameters critical to the prediction of a successful electrospinning process from solution properties is essential, yet, not easy in the case of biopolymers. In this study, we attempted to present a broad perspective by simultaneously evaluating the effect of eight different parameters, namely zero shear viscosity, tip viscosity, elastic modulus, phase angle, cohesive energy, pH, conductivity, and surface tension, on the formation of smooth pectin nanofibers. Our results showed that (1) the viscosity of the solution is not an indication of jet formation, but once the jet is formed, high zero shear viscosity and high tip viscosity are required to maintain a dominant whipping instability for smooth nanofiber formation and (2) while evaluating the elasticity of the spinning solutions, comparing only the elastic modulus values would be misleading, since low phase angle values are also necessary for pectin solutions to be electrospun into nonbeaded fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48294.