<p>Nowadays, various forms of organosilane materials are well established in the field of regenerative medicine, but interestingly, fibrous organosilanes have yet to be described. So far, technological obstacles prevent the preparation of such fibrous materials without any presence of spinnability-supporting organic polymers, various types of surfactants, or non-polar organic solvents, which are in many cases highly toxic and economically inconvenient. Recently, these obstacles were overcome by a complex, yet simple, technology combining different science perspectives from supramolecular chemistry through material science to tissue engineering. This paper suggests a synthesis of two biomedically promising monomeric organosilane precursors, <i>N</i>,<i>N</i>´-<b>b</b>is(3-(<b>t</b>riethoxysilyl)propyl)<b>t</b>erephthalamide (<b>BTT</b>) and <i>N</i>,<i>N</i>´-<b>b</b>is(3-(<b>t</b>riethoxysilyl)propyl)<b>p</b>yridine-2,6-dicarboxamide (<b>BTP</b>), which are submitted to a sol-gel process combined with subsequent electrospinning technology. Such a unique procedure not only allows the preparation of toxic-free organosilane fibrous mats by suitable adjustment of sol-gel and electrospinning parameters but also simplifies material production via a one-pot synthesis approach further tuneable with appropriate organosilane precursors. The BTT and BTP fibrous materials prepared displayed not only a promising interface among the materials and 3T3 fibroblast cell lines but moreover, the interaction of nanofibrous materials with stem cells has yielded encouraging outcomes. Stem cell adhesion, proliferation, and differentiation were notably enhanced in the presence of these materials, suggesting a supportive microenvironment conducive to regenerative responses. The ability of the material to modulate the cellular behaviour of stem cells holds promising implications for the development of targeted and effective regenerative therapies.</p> Graphical Abstract <p></p>