Surface engineering of biomaterials could promote the osseointegration of implants. In this work, two types of hybrid sol-gel materials were developed to stimulate cell attachment, proliferation and differentiation of osteogenic cells. One type was synthesised from vinyl triethoxysilane (VTES) and tetraethyl-orthosilicate (TEOS) at different molar ratios, while the other from VTES and hydroxyapatite particles (HAp). Hybrid materials were systematically investigated using nuclear magnetic resonance, Fourier transform infrared spectroscopy and contact angle metrology. The biocompatibility and osseoinduction of the coatings were evaluated by measuring mesenchymal stem cell proliferation using MTT assays and analysing the mineralised extracellular matrix production by quantifying calcium-rich deposits. The results highlighted the versatility of these coatings in obtaining different properties by changing the molar ratio of the VTES:TEOS precursors. Thus, mineralisation was stimulated by increasing TEOS content, while the addition of HAp improved cell proliferation but worsened mineralisation.