| Sumario: | The dehydrogenative coupling of hydrosilanes with alcohols or water is a fundamental transformation in organosilicon chemistry, enabling the synthesis of alkoxysilanes, silanols, and siloxanes—key materials for coatings and adhesives. Traditionally, these reactions have relied on catalysts based on platinum group metals, which are costly and scarce. The development of Earth‐abundant metal (EAM) catalysts offers a sustainable and cost‐effective alternative. This concept article highlights recent advancements in homogeneous EAM catalysis for these transformations, focusing on mechanistic insights, reactivity trends, and catalytic efficiencies. Catalysts based on manganese, iron, cobalt, copper, or zinc are reshaping the field by offering efficient and selective processes for the synthesis of alkoxysilanes, silanols, and siloxanes. Moreover, a key feature of these catalytic systems is their ability to generate dihydrogen as a byproduct, offering potential applications in hydrogen storage and utilization. Despite the good performances of EAM catalysts in the hydrolysis or alcoholysis of silanes, challenges remain, including improving turnover numbers, substrate scope, and catalyst stability. Future developments integrating computational and experimental approaches will be key to optimizing these systems.
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