Electrospun poly (epsilon-caprolactone) (PCL) nanofibers containing molecularly imprinted polymer (MIP) nanoparticles based on methacrylic acid (MAA) were prepared for controlled release of dexamethasone (Dexa). First, the MIPs consisting of Dexa were synthesized via precipitation polymerization. Their recognition sites formation and thermal properties were investigated by FTIR and TGA tests, respectively. The results showed that by selecting a monomer: template (MAA:Dexa) molar ratio of 6 : 1, MIP nanoparticles were produced with imprinting factor of 1.80. The FESEM and TEM images showed the MIPs average diameter of 394 +/- 9.7 nm and appropriate immobilization of them in PCL nanofibers, respectively. Moreover, the cumulative release of Dexa from the MIP-loaded nanofibrous samples was studied by UV-vis spectrophotometry and revealed a suitable controlled release of the drug during four days. Afterward, Dexa release followed Higuchi model which indicated the main mechanism was governed by Fickian diffusion theory.