A novel non-hydrolytic sol–gel (NHSG) synthesis of mesoporous tin silicate xerogels is presented. The polycondensation between silicon tetraacetate, Si(OAc)₄, and tetrakis(diethylamido)tin, Sn(NEt₂)₄, resulting in acetamide elimination leads to tin silicate xerogels containing Si–O–Sn linkages. The addition of Pluronic P123 or F127 templates provides homogeneous stiff gels that are, after template removal by calcination at 500 °C in air, converted to stable mesoporous silica xerogels with large surface areas (476 m² g⁻¹) and dispersed SnO₂ nanoparticles (6–7 nm). Heat treatment of the as-prepared tin silicate gels in an inert N₂ atmosphere leads to reduction and transformation to Sn nanoparticles (70–150 nm) embedded in a silica–carbon matrix. The composition and morphology of the xerogels, volatile reaction byproducts, and thermal transformations were followed by elemental analyses, IR spectroscopy, thermal analysis TG-DSC, nitrogen adsorption measurements, solid-state NMR spectroscopy, DRUV-vis spectroscopy, electron microscopy, and HT powder XRD. The SnO₂–SiO₂ xerogels were tested as potential catalysts for aminolysis of styrene oxide with aniline and for the Meerwein–Ponndorf–Verley reduction of 4-tert-butylcyclohexanone. The resulting reaction systems displayed good activity and selectivity.