Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(≡CtBu)(CH2tBu)3 with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(≡SiOH)(≡SiNH2)], leads to [(≡SiNH2−)(≡SiO−)W(≡CHtBu)(CH2tBu)2] and [(≡SiNH2−)(≡SiO−)W(=CHtBu)2(CH2tBu). Variable temperature, 1H–1H 2D double-quantum, 1H–13C HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(≡Si−OH)(≡Si−NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface–complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 °C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.