Mesoporous Ga-silicates were efficiently prepared using a sustainable and continuous synthesis procedure. The novel solids showed record activity in the synthesis of solketal from glycerol and acetone. Three different Si/Ga ratios of 34, 74 and 148 were investigated and all materials displayed favorable features for catalytic applications such as high surface area and calibrated mesoporosity. The insertion of Ga predominantly as single site in tetrahedral coordination in the silica framework was elucidated by XPS, using the Auger parameter of Ga in a Wagner plot representation. The speciation of Ga was further clarified using solid state 71Ga NMR spectroscopy, confirming the formation of mainly isolated Ga species. Consistently, the aerosol-made Ga-silicates displayed outstanding turnover frequencies (up to 677 h-1) and selectivity, markedly outcompeting other reference metallosilicate catalysts reported in literature. Moreover, the most active catalyst was successfully reused in multiple catalytic cycles thus proving its stability under the selected reaction conditions.