Bone tissue engineering success strongly depends on our ability to develop new materials combining osteoconductive, osteoinductive and osteogenic properties. Recent studies suggest that biomaterials incorporating silanol (Si-OH) groups promote and maintain osteogenesis. The purpose of the present research work was to provide evidence that using wet-spinning technologies and a calcium silicate solution as a coagulation bath, it was possible to develop an in situ functionalization methodology to obtain 3D wet-spun fibre meshes with Si-OH groups, through a simple, economic and reliable process. SPCL (blend of starch with polycaprolactone) fibre meshes were produced by wet-spinning, using a calcium silicate solution as a non-solvent and functionalized in situ with Si-OH groups. In vitro tests, using goat bone marrow stromal cells (GBMSCs), showed that SPCL-Si scaffolds sustained cell viability and proliferation. Furthermore, high ALP activity and matrix production indicated that Si-OH groups improve cellular functionality towards the osteoblastic phenotype. Using this methodology, and assembling several wet-spun fibre meshes, 3D meshes can be developed, aiming at designing osteoconductive/osteoinductive 3D structures capable of stimulating bone ingrowth in vivo. Copyright (C) 2010 John Wiley & Sons, Ltd.