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Core-shell polycaprolactone/polycaprolactone (PCL/PCL) and polycaprolactone/polyvinyl acetate (PCL/PVAc) electrospun fibers loaded with synthesized nanohydroxyapatite (HAn) were lased treated to create microporosity. The prepared materials were characterized by XRD, FTIR, TEM and SEM. Uniform and randomly oriented beadless fibrous structures were obtained in all cases. Fibers diameters were in the 150–300 nm range. Needle-like HAn nanoparticles with mean diameters of 20 nm and length of approximately 150 nm were mostly encase inside the fibers. Laser treated materials present micropores with diameters in the range 70–120 μm for PCL-HAn/PCL fibers and in the 50–90 μm range for PCL-HAn/PVAC material. Only samples containing HAn presented bioactivity after incubation during 30 days in simulated body fluid. All scaffolds presented high viability, very low mortality, and human osteoblast proliferation. Biocompatibility was increased by laser treatment due to the surface and porosity modification.