Polyvinyl alcohol (PVA) with an average molecular weight between 40,500 and 155,000 g/mol was electrospun with a calcium phosphate based sol. The sol was prepared by reacting triethyl phosphite and calcium nitrate and was directly added to an aqueous solution of PVA. This mixture was electrospun at a voltage of 20 kV. The results indicate that the sol was distributed uniformly in the PVA fibers, whose diameter was on the order of 2 mu m. This electrospun structure was calcined at 600 degrees C for 6 h to obtain a residual inorganic, fibrous network, with fiber diameters between 200 and 800 nm. The fibrous structure consists predominantly of hydroxyapatite with an average crystal size of almost 10 to 30 nm. A variety of structures including non-woven mats of solid or micro-porous hydroxyapatite fibers and highly porous scaffolds could be obtained by varying the polymer molecular weight and the sol volume fraction. These structures can have many potential uses in the repair and treatment of bone defects, drug delivery and tissue engineering. (C) 2006 Elsevier B.V. All rights reserved.