Biocompatibility in research and development of advanced prosthetics is a current problem faced by medical researchers. Hydroxyapatite (HA) is a natural ceramic (responsible for strength and stability in the human skeletal system) operable as a biocomposite coating to improve the biocompatibility of materials such as silicon nitride, typically used for bone replacement. In this study, polymer based composites were prepared by electrospinning HA with a biocompatible polymer for the development of a structurally stable casing for prosthetic devices. Presented in this paper is the morphological and structural study of electrospun polymer-HA mats. Electrospun mats were calcinated at the phase transformation temperature of HA revealing pure HA wires with diameters just under 1 mu m and lengths of the order of 10 to 50 mu m. Results have outlined the dispersion mechanism of HA electrospun with polyvinylpyrrolidone (PVP) and cellulose acetate (CA) in varying solvents to discern the effects of acidic additives and electrospinning on the production of HA wires. Copyright (c) 2006 John Wiley & Sons, Ltd.