The olefin metathesis activity of silica-supported molybdenum oxides depends strongly on metal loading and preparation conditions, indicating that the nature and/or amounts of the active sites vary across compositionally similar catalysts. This is illustrated by comparing Mo-based (pre)catalysts prepared by impregnation (2.5-15.6 wt % Mo) and a model material (2.3 wt % Mo) synthesized via surface organometallic chemistry (SOMC). Analyses of FTIR, UV-vis, and Mo K-edge X-ray absorption spectra show that these (pre)catalysts are composed predominantly of similar isolated Mo dioxo sites. However, they exhibit different reaction properties in both liquid and gas-phase olefin metathesis with the SOMC-derived catalyst outperforming a classical catalyst of a similar Mo loading by ×1.5-2.0. Notably, solid-state ⁹⁵Mo NMR analyses leveraging state-of-the-art high-field (28.2 T) measurement conditions resolve four distinct surface Mo dioxo sites with distributions that depend on the (pre)catalyst preparation methods. The intensity of a specific deshielded ⁹⁵Mo NMR signal, which is most prominent in the SOMC-derived catalyst, is linked to reducibility and catalytic activity. First-principles calculations show that ⁹⁵Mo NMR parameters directly manifest the local strain and coordination environment: acute (SiO-Mo(O)₂-OSi) angles and low coordination numbers at Mo lead to highly deshielded ⁹⁵Mo chemical shifts and small quadrupolar coupling constants, respectively. Natural chemical shift analyses relate the ⁹⁵Mo NMR signature of strained species to low LUMO energies, which is consistent with their high reducibility and corresponding reactivity. The ⁹⁵Mo chemical shifts of supported Mo dioxo sites are thus linked to their specific electronic structures, providing a powerful descriptor for their propensity toward reduction and formation of active sites.