Non-surfactant-induced synthesis of mesoporous silica nanoparticles (MSNPs) is gaining increasing interest because of their low toxicity and simple purification compared to conventional surfactant-based methods. Tannic acid (TA), considered as a glucose-derived polyphenol, was first employed a few years ago and has attracted great research interest. Despite recent progress, the mechanisms resulting in the porous structure remain to be elucidated. In this work, we have employed TA and four structurally related polyphenols (gallic acid, ethyl gallate, eudesmic acid, and quercetin) to elucidate the effect of the chemical structure and properties of polyphenols on their templating ability. Our results unravel the mechanism of MSNP formation templated by TA, which form a supramolecular framework as the skeleton for the silica species to attach. The structure of the supramolecular network results in irregular pores. Additionally, the pK(a) value of the templates may be accounted for the particle size. Small-angle X-ray scattering was used to provide precise information on the morphology, especially the porosity of the resulting MSNPs in addition to electron microscopy, dynamic light scattering, nitrogen adsorption and desorption Brunauer-Emmett-Teller method, and thermogravimetric analysis.