The reaction pathways on supported catalysts can be tuned by optimizing the catalyst structures, which helps the development of efficient catalysts. Such design is particularly desired for CO2 hydrogenation, which is characterized by complex pathways and multiple products. Here, we report an investigation of supported cobalt, which is known for its hydrocarbon production and ability to turn into a selective catalyst for methanol synthesis in CO2 hydrogenation which exhibits good activity and stability. The crucial technique is to use the silica, acting as a support and ligand, to modify the cobalt species via Co‒O‒SiOn linkages, which favor the reactivity of spectroscopically identified *CH3O intermediates, that more readily undergo hydrogenation to methanol than the C‒O dissociation associated with hydrocarbon formation. Cobalt catalysts in this class offer appealing opportunities for optimizing selectivity in CO2 hydrogenation and producing high-grade methanol. By identifying this function of silica, we provide support for rationally controlling these reaction pathways.