The properties of hybrid aminopropyltriethoxysilane-tetraisopropylorthotitanate (APTS-TIPT) platforms prepared by a sol-gel route have been explored, and their biocompatibility was assayed after culture of human mesenchymal stem cells (hMSCs). The organic content of this material was observed to be preferably surface-oriented as indicated by microanalytical techniques. Furthermore, the surface showed characteristic amino-silane bands when explored by Raman spectroscopy as well as indications of silane and titanate condensation. Surface activity of the amino groups was probed by ultraviolet-visible spectroscopy imine derivatization and chemical force spectroscopy, showing a pH-dependent surface charge-induced potential. hMSCs cultured onto these surfaces showed relevant differences with respect to their behavior on gelatin-coated glass plates. Even if with a lower proliferative rate than controls, the cells develop long cytosolic prolongations in osteogenic differentiation medium, thus, supporting the idea of an APTS-TIPT stimulated process.