Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.