A series of molybdenum alkylidyne silyloxy N-heterocyclic carbene (NHC) complexes of the general formula [Mo(�C-(R))(OSiPh 3 ) 3 (NHC)] (R = tBu, 4-methoxyphenyl, 2,4,6-trimethylphenyl; NHC = 1,3-diisopropylimidazol-2-ylidene, 1,3-dicyclohexylimidazol-2-ylidene, 1,3-dicyclohexyl-4,5-dihydroimidazol-2ylidene, 1,3-dimethylimidazol-2-ylidene, 1,3-dimethyl-4,5-dichloroimidazol-2-ylidene) was synthesized. Single crystal X-ray analyses revealed that with increasing steric demand of the alkylidyne group, enhanced air-stability of the complexes in the solid-state is achieved with the most stable complex (R = 2,4,6trimethylphenyl, NHC = 1,3-diisopropylimidazol-2-ylidene) being stable in air for 24 h without showing signs of decomposition in 1 H NMR. In contrast to previously reported air-stable molybdenum-based complexes, the novel catalysts proved to be highly active in alkyne metathesis, allowing for turnover numbers (TONs) of up to 6000 without further activation, and tolerant towards several functional groups such as tosyl, ether, ester, thioether and nitro moieties. Their air stability allows for facile handling of the catalysts in air and even after exposure to ambient atmosphere for one week, the most stable representative still displayed high productivity in alkyne metathesis.