Current efforts in bone tissue engineering have as one focus the search for a scaffold material that supports osteoblast proliferation, matrix mineralization, and, ultimately, bone formation. Electrospraying of polymer solutions has enabled the engineering of porous materials to meet current challenges in bone replacement therapies. Porous scaffolds of poly( -caprolactone)/poly(diisopropyl fumarate) compatibilized blend for bone tissue engineering were obtained by electrospraying technique in order to create a better osteophilic environment for the growth and differentiation of osteoblasts. Non-porous films having smooth surface were obtained by casting and used for comparison purposes. Studies on cell-scaffold interaction were carried out by culturing two osteoblastlike cell lines, MC3T3E1 and UMR106, on three-dimensional scaffolds and two-dimensional films. Growth, proliferation, and differentiation (alkaline phosphatase activity) of osteoblasts, were assessed. Scaffolds displayed a highly porous structure with interconnected pores formed by polymer microparticles, and higher hydrophobicity than the observed in non-porous films. The adhesion, proliferation and alkaline phosphatase activity of cells grown on the porous scaffolds increased significantly in comparison to those observed on flat films. The rough surface morphology of this novel scaffold enhances osteoblast response. These results suggest that electrosprayed porous scaffolds may be potentially used as tissue engineering scaffolds with high bone regenerative efficacy.