We demonstrate that electrospinning is a simple and efficient method of preparing pure polymer complexes. Such complexes are often difficult to prepare by conventional methods because of the kinetically favored crystallization of small molecules. As proof-of-concept examples, nanofibers of the complexes of poly(ethylene oxide) with hydroquinone and sodium thiocyanate (NaSCN) were produced. Infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry were used to confirm the purity of the electrospun complexes and to establish the general applicability of this new strategy. It is concluded that the fast solvent evaporation is the critical factor enabling pure complex formation. This work should enable a better study of host/guest polymer complexes, for instance in the context of ionic conduction in the solid state.