Materials for bone defect filling should have 3D macroporous structure and be flexible to be packed into complex defects with limited entrance space. Tissue engineering scaffolds should also mimic the structure and morphology of the host tissue. Electrospinning is a versatile technique to produce materials with micro/nanofibrous structure, large surface area and high porosity. Electrospun materials are very promising for tissue engineering due to the possibility of mimicking the fibrous structure of natural extra cellular matrix (ECM). Siloxane-containing vaterite (SiV)/poly (L-lactic acid) (PLLA) hybrids (SiPVH) with controlled silicate and calcium ions releasing ability has been produced in our group. They have also demonstrated good cell infiltration into the electrospun hybrid materials that had fiber diameters greater than 10 μm. However, these electrospun hybrid materials were planar (2D) and are not suitable for large defect regeneration. In this work, the development of a fabrication technique for the production of 3D cotton wool-like structures with fiber diameter in the range of 10 μm was performed. SiPVH cotton wool-like structure containing 0, 30 and 60 wt % SiV were prepared by blowing air in the direction perpendicular to fiber spinning. Si-vaterite particles and small pores were found on the surface of the fibers. The fiber diameter of the samples were found to be in the range of 10 ~ 20 μm. Stretch tests showed more than 50 % extension for the SiPVH cotton wool-like material containing 30 wt % SiV (SiPVH30). This extension was similar to that observed for the PLLA cotton wool-like material. The results suggest that the SiPVH30 cotton wool-like material are good candidates for bone tissue engineering scaffolds.