Understanding the spatial distribution of functionalities on surfaces with atomic-scale resolution is very important for catalytic applications, yet very challenging for analytical inquiry. Recent advances in solid-state nuclear magnetic resonance (SSNMR), especially in dynamic nuclear polarization and fast magic-angle spinning, offer new tools for examining this longstanding problem. The aim of this Perspective is to showcase how these SSNMR methods can shed light on the uniformity of surface functionalities deployed on mesoporous silica-based catalysts using post-synthesis grafting and co-condensation methods. The results are discussed in the context of earlier landmark studies on the spatial distributions of surface species using probe molecules and reactions.