Organosilicons for surface modification are gaining prominence because of their easy and rapid preparation, high availability, and effective modification for varying interfacial properties. However, their implementation has been humbled by poor control of the packing density, thickness, and molecular structures due to the uncontrollable hydrolysis and condensation. This study reports for the first time new functional silatrane chemistry for the precision deposition of a thin and homogeneous zwitterionic coating. Sulfobetaine silatrane (SBSiT) has a tricyclic caged structure and a transannular N → Si dative bond, which shows excellent chemical stability in the presence of water and an acid-modulated hydrolysis characteristic. Results from X-ray photoelectron spectroscopy indicate the progressive deposition of SBSiT on a silicon surface. Characterization using atomic force microscopy and ellipsometry shows the uniform and thin SBSiT films on silicon surfaces. The superior antifouling properties of SBSiT coatings were demonstrated by resisting bacterial and protein adsorption. More importantly, the stable and complete formation of the SBSiT coatings allows an accurate interpretation of the interfacial phenomena for sensing and nanomaterial applications.