A polymer-inorganic sol mixture has been used to develop interconnected and highly porous calcium phosphate networks, The inorganic sol was developed by reacting triethyl phosphite and calcium nitrate. The sol was directly added to an aqueous solution of PVA with molecular weights between 40,500 and 155,000 g/mol. This mixture was electrospun at a voltage of 20 kV to produce fibers, whose diameter was less than 1 gm. This electrospun structure was calcined at 600 degrees C obtain to a highly interconnected sub-micron fibrous network (fiber size similar to 200 nm) of calcium phosphate. The crystal size is on the order of 30 nm. Micropores could be introduced in each of the fibers by controlling the polymer molecular weight and the sol volume fraction. Such structures can have many potential uses in the repair and treatment of bone defects and in drug delivery. Published by Elsevier B.V.