This study deals with poly(lactic acid) (PLA), poly(ε‐caprolactone) (PCL), and their blend electrospun nanofibers (ESNF) as novel systems for the release of levetiracetam (LEV). Scanning electron microscopy demonstrated that the morphology of all samples is smooth and beads‐free. In addition, with increasing LEV content, the average diameters of PLA, PCL, and PCL/PLA ESNF enhanced by almost 69%, 41%, and 14%, respectively. FTIR spectroscopy was utilized to confirm the structure of polymer and drug, polymer‐drug interaction, and the observation of functional groups. The pore percentage was also diminished by adding LEV. The results of x‐ray diffraction revealed that the crystallinity decreased from 18.2%, 40.1%, and 21.5% for PLA, PCL, and PLA/PCL ESNF, respectively, to 15%, 31.2%, and 13.6% for the samples containing 18 wt% LEV. In addition, PLA ESNF containing 10 and 18 wt% LEV demonstrated a steady uptrend for drug release, while PCL and PLA/PCL ESNF containing 10 and 18 wt% LEV initially indicated an abrupt increase in drug release and then became steady. Moreover, drug release kinetics were evaluated using different models such as zero order, first order, Higuchi, and Korsmeyer‐Peppas models and the best model for predicting the drug release behavior was selected.