The silk fibroin/calcium phosphate composites were prepared by adding the different amount of Na(2)SiO(3) to assess the effect of silicon on the HA (hydroxyapatite) formation in the composites. FTIR and XRD results suggested that the inorganic phase was constituted mainly by the amorphous DCPD (dicalcium phosphate dehydrate), a precursor of HA in the bone mineral, when the composites were prepared at the final Na(2)SiO(3) concentration lower than 0.008%. Otherwise, HA was formed as the predominant one in the as-prepared composite, accompanied with a conformational transition in the organic phase of silk fibroin protein from silk I (alpha-helix and/or polyglycine II (3(1)-helix) conformations) to silk II (antiparallel beta-sheet conformation). SEM images showed the different morphologies with the samples, i.e., sheet-like crystals in the composites prepared at a low Na(2)SiO(3) concentration and rod-like bundles in other composites. The rod-like bundles were connected together to form the porous network, due to the fact that the HA crystals grew with the aggregation of silk fibroin, and further accreted onto the silk fibroin fibrils. TG curves indicated that the composites prepared with a certain amount of additional SiO (3) (2-) had the higher thermal stability because of its high molecular orientation and crystallinity, and high water-holding capacity due to the porous microstructure.