Interstellar silicates play a key role in star formation and in the origin of solar systems, but their synthetic routes have remained largely elusive so far. Here we demonstrate in a combined crossed molecular beam and computational study that silicon dioxide (SiO2) along with silicon monoxide (SiO) can be synthesized via the reaction of the silylidyne radical (SiH) with molecular oxygen (O2) under single collision conditions. This mechanism may provide a low-temperature path-in addition to high-temperature routes to silicon oxides in circumstellar envelopes-possibly enabling the formation and growth of silicates in the interstellar medium necessary to offset the fast silicate destruction.