The objective of this study was to investigate the adsorption/desorption behavior of oleuropein on different types of silk fibroin matrices including silk fibroin microfibers (MF), regenerated silk fibroin (RSF), and silk fibroin nanofibers (NF). Nanofibers with an average diameter of ranging between 24 and 326 nm were successfully prepared using the electrospinning technique. The effects of the silk fibroin concentration, the voltage applied and the distance between needle tip and collector plate on the morphology of the NF were investigated. The adsorption capacities of MF, RSF and NF were determined as 104.92, 163.07 and 228.34 mg oleuropein per gram of material, respectively. The percentage of initially adsorbed oleuropein that was desorbed was 86.08, 91.29 and 96.67% for MF, RSF and NF, respectively.