One of the key challenges in materials science is to control the size and shape of inorganic nanoparticles with a high degree of precision, as these parameters have a significant influence on the nanoparticles' properties and potential applications. Here, we describe the preparation of highly monodisperse silica nanoparticles smaller than 5 nm in diameter by using self-assembled, hollow, spherical compounds as 'endo-templates'. These coordination complexes with pendant sugar groups lining their interiors-assembled from 12 metal ions and 24 bis-pyridyl ligands containing glucose substituents-acted as structurally well-defined templates for the sol-gel condensation of alkoxysilanes. The polydispersities of the silica nanoparticles made with this method approached unity, with M(w)/M(n) < 1.01. The component ligands are modified easily, which enables an accurate expansion of the coordination complex and the subsequent control of the monodisperse silica nanoparticles that span molecular weights of 5,000 to 31,000 Da (corresponding to 2-4 nm in diameter). This method could be applicable to the preparation of other inorganic nanoparticles.