Trace amounts of ionic calcium and silicon species have been reported to stimulate the proliferation, differentiation, and mineralization of bone-forming cells. Composite materials comprising siloxane-doped calcium carbonate (vaterite) particles and poly(L-lactic acid) have been developed [siloxane-poly(lactic acid)-vaterite hybrid-composite, SiPVH] so far; they were designed such that calcium and silicate ions are gradually released from SiPVH and they show the chronic effects of ions on cellular activities. In the present work, SiPVH with a 3D cotton-like structure was prepared by electrospinning to obtain the major advantages of excellent bioactivity and ease of handling for bone filling surgery. The diameter of the fibrous skeletons that form structure of the cotton-like SiPVH was controlled to ~10 μm to achieve cellular migration into the spaces between fibers. The resulting cotton-like SiPVH showed good flexibility. The fiber surface was coated rapidly with numerous particles of several hundred nanometers in size by alternate soaking in CaCl(2) and Na(2)HPO(4). The treated cotton-like material, which released calcium and silicate ions gradually, showed good cellular migration behavior into the 3D structure in cell culture tests using murine osteoblast-like MC3T3-E1 cells.