The climate situation that the planet is experiencing, mainly due to the emission of greenhouse gases, poses great challenges to mitigate it. Since CO2 is the most abundant greenhouse gas, it is essential to reduce its emissions or, failing that, to use it to obtain chemicals of industrial interest. In recent years, much research have focused on the use of CO2 to obtain methanol, which is a raw material for the synthesis of several important chemicals, and dimethyl ether, which is advertised as the cleanest and highest efficiency diesel substitute fuel. Given that the bibliography on these catalytic reactions is already beginning to be extensive, and due to the great variety of catalysts studied by the different research groups, this review aims to expose the most important catalytic characteristics to take into account in the design of silica-based catalysts for the conversion of carbon dioxide to methanol and dimethyl ether.