A highly hydrothermally stable microporous network material has been developed that can be applied in energy-efficient molecular sieving. The material was synthesized by employing organically bridged monomers in acid-catalysed sol–gel hydrolysis and condensation, and is composed of covalently bonded organic and inorganic moieties. Due to its hybrid nature, it withstands higher temperatures than organic polymers and exhibits high solvolytical and acid stability. A thin film membrane that was prepared with the hybrid material was found to be stable in the dehydration of n-butanol at 150 °C for almost two years. This membrane is the first that combines a high resistance against water at elevated temperatures with a high separation factor and permeance. It therefore has high potential for energy-efficient molecular separation under industrial conditions, including the dehydration of organic solvents. The organically bridged monomers induce increased toughness in the thin film layer. This suppresses hydrolysis of Si–O–Si network bonds and results in a high resistance towards stress-induced cracking. The large non-hydrolysable units thus remain well incorporated in the surrounding matrix such that the material combines high (pore) structural and mechanical stability. The sol mean particle size was found to be a viable parameter to tune the thickness of the membrane layer and thus optimize the separation performance. We anticipate that other hybrid organosilicas can be made in a similar fashion, to yield a whole new class of materials with superior molecular sieving properties and high hydrothermal stability.