Ultrafine fibers manufactured through electrospinning are a frontrunner for advanced fiber applications, but transitioning from potential to commercial applications for ultrafine fibers requires a better understanding of the behavior of polymer solutions in electrospinning to enable the design of more complex spinning dopes. In complex fluids, there are viscoelastic stresses and microstructural transitions that alter free surface flows. These may not be seen in shear rheology; therefore, an in-depth analysis of the extensional rheological behavior must be performed. In this work, we use dripping-onto-substrate rheometry to characterize the extensional viscosities of electrospinning dopes from four polymer solutions commonly used in electrospinning (low- and high-molecular-weight polyvinylpyrrolidone in methanol and water as well as poly­(ethylene oxide) and poly­(vinyl alcohol) in water). We link the electrospinnability, characterized through fiber morphology, to the extensional rheological properties for semidilute and entangled polymer solutions and show that high-surface-tension solvents require higher extensional viscosities and relaxation times to form smooth fibers and that the Deborah and Ohnesorge numbers are a promising method of determining electrospinnability. Through this tie between solvent characteristics, viscoelasticity, and electrospinnability, we will enable the design of more complex spinning dopes amenable to applications in wearable electronics, pharmaceuticals, and more.