Silicon on silica materials are ubiquitous in 21st century technology. From nanoparticles to integrated circuits, these systems are integral for modern semiconductor fabrication. While the Si-SiO2 interface is often (incorrectly) presumed to be stable, the direct reduction of silica by silicon is possible at high temperatures, resulting in the evolution of silicon monoxide (SiO) gas. Under appropriate conditions, this somewhat unexpected reaction can complicate solid state nanomaterial syntheses by etching away the desired products. This report describes an investigation into the SiO evolution reaction by interrogation of powdered Si-SiO2 mixtures before and after thermal treatment. The impacts of processing temperature, time, and sample composition are examined and discussed. Of particular importance, this investigation reveals the underappreciated role of silica crystallinity (cristobalite) in this solid-state reaction under comparatively low temperature conditions (ca. 1200 °C). With an improved understanding of SiO evolution, we hope to inspire new creative pathways for Si-SiO2 interface manipulation.