Sol-gel bonds were produced between smooth, clean silicon or polycrystalline alumina substrates by spin-coating solutions containing partially hydrolysed silicon alkoxides onto both substrates. The two coated substrates were assembled and the resulting sandwich was fired at temperatures ranging from 300 to 600°C. The influence of the sol-gel chemistry on the film microstructure and interfacial fracture energy was investigated using a wide range of techniques, including ellipsometry, FTIR, TG-DTA, rheology, TEM and micro-indentation. For silicon wafers, an optimum water-alkoxide molar ratio of 10 and hydrolysis water pH of 2 were found. Such conditions led to relatively dense films (>90%), resulting in bonds with significantly higher fracture energy (3.5 J/m2) than those obtained using classical water bonding (typically 1.5 J/m2). Aging of the coating solution was found to decrease the bond strength. Poly-crystalline alumina substrates were similarly bonded at 600°C; the optimised silica sol-gel chemistry yielded interfaces with fracture energy of 4 J/m2.