Characterizing the parameters critical for the prediction of a successful electrospinning process from solution properties is essential, yet, not easy in the case of biopolymers due to their distinct and complicated natures. In this study, we attempted to understand the effect of rheological parameters on the formation of smooth pectin nanofibers. Low methyl esterified amidated pectin was blended with polyethylene oxide (PEO) at three different molecular weights (600, 1000, and 2000 kDa). Non-beaded nanofibers were obtained only when PEO2000 was used in the blends. Since the pH, conductivity, and surface tension of the blends with PEO2000 did not differ from other blends at the same pectin concentration, the rheological properties were found to significantly correlate with the electrospinnability of pectin/PEO blends. High zero shear viscosity and high elastic modulus values together with low phase angle values were essential for pectin solutions to be electrospun into non-beaded continuous fibers.