The design of appropriate materials is required for biomedical applications (e.g. drug delivery systems) in improving people's health care processes. This study focused on the incorporation of nanosized hydroxyapatite (n-HA) with different ratios (ranging from 0.1 wt% to 0.5 wt%) into the poly (epsilon-caprolactone)/ poly (ethylene oxide) (PCL/PEO) blend matrix loaded or unloaded with curcumin. Composite fibrous material systems were successfully fabricated by the electrospinning technique without the occurrence of bead defects. In addition to the morphological and physicochemical properties of the material systems obtained, the in vitro curcumin release performance was investigated. Further, anti-cancer activity against breast cancer cell line (MCF-7) was examined by MTT assay. Fourier transform infrared spectroscopy and X-ray diffraction characterizations of the fabricated fibrous materials exhibited the interaction of PCL/PEO, n-HA, and curcumin. The 0.3 wt% n-HA incorporated fibrous materials showed a much slower curcumin release manner along with the highest cytotoxicity against MCF-7 cells. The findings obtained from this research are expected to contribute to the appropriate design of nanofiber-based composite materials not only for drug delivery systems but also for the fabrication of biomaterials toward different biomedical applications.