This work reports the production of hydroxyapatite (HA) sub-micron fibers by combining electrospinning and a non-alkoxide sol-gel system, using cheap precursors. Phosphorus pentoxide (P(2)O(5)) and calcium nitrate tetrahydrate (Ca(NO(3))(2)center dot 4H(2)O) were used as precursors of phosphorus and calcium, respectively. The fibers were electrospun from a mixture of the gel formed from the system Ca(NO(3))(2)center dot 4H(2)O/P(2)O(5) with polymeric solutions of polyvinylpyrrolidone (PVP) in water and ethanol/water mixtures. The fibers were analyzed for their morphology (Scanning Electron Microscopy. SEM), chemical composition (Fourier Transform Infrared Spectroscopy, FTIR) and structure (X-ray diffraction, XRD). The fibers obtained were composed mainly of type B carbonated HA with traces of beta-tricalcium phosphate (beta-TCP). SEM analysis revealed that increasing the concentration of water in the solvent system, used in the preparation of electrospinning solutions, led to fibers with smaller diameters and narrower diameter distribution. (C) 2011 Elsevier B.V. All rights reserved.