The combination of first‐row transition compounds or nanoparticles with silica‐based supports offers a great possibility for catalyst design. In particular, iron, cobalt and nickel‐based materials rise in attention due to their availability, low cost and interesting reactivity, enabling transformations that are not possible with noble metals. Different support strategies exist where mesoporous silica‐based supports are of particular interest due to their morphology and stability. Their high surface area, tunable pore size and volume and both, thermal and chemical stability, are of great interest in terms of catalyst adsorption and reactants diffusion. The state of the art on the catalyzed transformations to attain fine chemicals is nowadays explored from a sustainable point of view. However, up to now, it is difficult to predict or understand the key features in silica supported first‐row transition metals‐based catalyst, despite the fact that there are widely applied. The rational tailoring of nanosized materials immobilized on silica‐based supports and their application in catalysis requires to be reviewed.