A precursor solution containing poly(vinyl alcohol) and a calcium phosphate sol is used to produce fibers of hydroxyapatite. The mixture is electrospun at a voltage of 20 kV and the resultant structure is calcined at 600 degrees C for 6 h. Experiments were conducted for polymer molecular weight (M-W) between 9500 and 155 000 g/mol and sol volume fractions (V-S) between 0% and 83%. The results indicate that the electrospun fiber diameter can be correlated to the solution viscosity. The polymer molecular weight and sol volume fraction have a significant effect on the ceramic structure. Highly interconnected solid or porous hydroxyapatite fibers with diameters between 200 and 500 nm and crystal sizes between 30 and 50 nm can be produced by controlling M-W and V-S.