The development of fibers with desired drug release properties has gained a high research interest for water-soluble drugs with controlled drug delivery systems obtained by coaxial electrospinning technique. The objective of this study is to achieve the controlled-release of doxycycline hyclate (DOXH) from the fabricated electrospun fibers. In this case, three different electrospun core/shell fibers have been successfully fabricated using this technique and the model drug, DOXH, has been entrapped in the core layers. The results of the structural properties and in vitro release studies have been compared with electrospun monostructural fibers fabricated by conventional electrospinning technique. Scanning electron microscopy and transmission electron microscopy images have proved that the fabricated electrospun fibers have core/shell structures. Fourier transform infrared spectroscopy has shown convenient interaction and compatibility between polymers and the model drug. X-ray diffraction analysis has revealed that all the encapsulated DOXH are transferred into amorphous physical state and lost its crystalline state in the fibers. Moreover, drug release studies have demonstrated that the electrospun core/shell fibers show a better-controlled release than the monostructural fibers. It can be concluded that the fibers obtained by blending hydrophilic and hydrophobic polymers such as poly(epsilon-caprolactone) and poly(ethylene oxide) in both shell and core sides are promising candidate for controlled drug release.