Sildenafil citrate (SC) has proved to be an effective and inexpensive drug for the treatment of pulmonary arterial hypertension (PAH). This study aims to synthesize electrospun, submicron fiber scaffolds of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) loaded with SC for fast drug dissolution and its potential use in the treatment of PAH. These fiber scaffolds were prepared through the electrospinning technique. The chemical composition of the nanofibers was analyzed by Fourier transform infrared spectroscopy. Thermal stability was studied by thermogravimetric analysis and polymeric transitions by differential scattering calorimetry. Surface analysis of the nanofibers was studied by field emission scanning electron microscopy. The wetting and dissolution time of the scaffolds and drug release rate were studied as well. The drug-loaded PVP fibers showed better quality regarding size and homogeneity compared to drug-loaded PVA fibers. These fibers encapsulated approximately 2.5 mg/cm2 of the drug and achieved immediate controlled released rate, which is encouraging for further studies leading to an alternative treatment of PAH in children.