Heterogeneous catalysts fulfill vital roles in industrial processes; however, the nature of the catalytic surfaces, typically either containing a low abundance of active sites or being amorphous in nature, leads to difficulties when attempting to study the structure of the active sites. In this work, we show how making use of fast MAS ssNMR allows one to efficiently detect well-resolved 1H-detected spectra of heterogeneous catalysts. This approach was applied to study the structure of surface species resulting from the grafting of VO(OiPr)3 onto a partially dehydroxylated silica using the surface organometallic chemistry approach. The use of 1H sensitivity enabled detection of various hetero- and homonuclear correlation spectra in order to study the structure of this system and to resolve the structure of the grafted vanadium complex. More specifically, VO(OiPr)3 grafts through both protonolysis and opening of siloxane bridges to generate a bis-grafted species.