Bone tissue is a complex structure with the capacity to self-regenerate and responsible for different functions in our body. However, when bone integrity is disturbed, its self-regenerative capacity is lost. The available treatments are based on bone grafts and other bone substitutes which possess several limitations. Herein, a new approach to mimic the extracellular matrix of bone and cellular microenvironment was developed in this work. Therefore, an electrospinning apparatus was used to produce poly(ε-caprolactone), polyethylene oxide-sodium alginate and poly(vinyl)pirrolidone nanofibers. Subsequently, the same procedure was used for coating the alginate scaffold. In addition, poly(ε-caprolactone) electrospun nanofiber membranes were also produced and evaluated for phase separation applications. Membranes specific properties, such as pore size, fibers diameter and surface interactions were studied. The biological properties of the coated scaffolds were evaluated through in vitro cytotoxicity assays. The results showed that all the coated scaffolds had their biological performance improved. The membranes showed to be good candidates for phase separation area.