Papaverine hydrochloride loaded electrospun fibers were prepared for buccal drug delivery with the aim of improving the oral bioavailability of the crystalline drug, which can be achieved by the increased solubility and by the circumvention of the intensive first pass metabolism. The water soluble hydroxypropyl cellulose (HPC) was chosen as a mucoadhesive polymer. In order to improve the electrospinnability of HPC, the also mucoadhesive poly(vinyl alcohol) (PVA) was used. During the experiments, the total polymer concentration was kept constantly at 15% (w/w), and only the ratio of the two polymers was changed. Five different HPC:PVA ratios (5:5, 6:4, 7:3, 8:2, 9:1) were examined. Combination of rheological measurements and molar reflectance characterization with scanning electron microscopy was applied for the determination of the optimum composition of the gels for fiber formation. The crystalline-amorphous transition of papaverine hydrochloride was also tracked by Fourier transform infrared spectroscopy. A correlation was found between the macrostructural properties of the polymer solutions and their electrospinnability and the consequent morphology of the resultant samples. Along with the changes of the polymer ratio, the corresponding morphology of the electrospun samples also varied. With decreasing HPC ratio of the system, a transition from the spray-dried film-like structure through fibrous film to fibers was observed. Polymer solutions of the lowest elasticity and smallest intermolecular interactions contributed to the best fiber characteristics of the samples. The results enable the determination of the polymer ratio for the formation of applicable quality of electrospun fibers. According to the results 5:5 and 6:4 polymer ratios enabled the best fiber performance.