Owing to recent progress in nanotechnology, the ability to tune the surface properties of metals has opened an avenue for creating a new generation of biomaterials. Here we demonstrate the successful development of a novel Ti-based nanoglass composite with submicron–nanometer-sized hierarchical glassy structures. A first exploratory study was performed on the application of the unique nanostructure to modulate osteoblast behaviors. Our results show that this Ti-based nanoglass composite, relative to conventional metallic glasses, exhibits significantly improved biocompatibility. In fact, a 10 times enhancement in cell proliferation has been achieved. To a great extent, this superior bioactivity (such as enhanced cell proliferation and osteogenic phenotype) is promoted by its unique hierarchical structures combining nanoglobules and submicron button-like clusters from collective packing of these nanoglobules. This nanoglass composite could be widely applicable for surface modifications by means of coating on various materials including BMGs, crystalline metals or ceramics. Therefore, our successful experimental testing of this nanostructured metallic glass may open the way to new applications in novel biomaterial design for the purpose of bone replacement.