Relative surface silanol (SiOH) concentration levels on low‐surface‐area crystalline silica (synthetic quartz crystal) have been determined using the static secondary ion mass spectroscopy (SIMS) technique. Various sample pretreatments, including water plasma (maximum silanol/hydroxylation), heating in a vacuum to ∼550°C, heating in a vacuum to > 1000°C (minimum silano/hydroxylation) and inert gas ion bombardment in ultrahigh vacuum (UHV), are examined. Both positive ion ration (SiOH+/SiO+, SiOH+/Si+) and a negative ion ratio (OH−/O−) were monitored as a function of temperature as the pretreated surface dehydroxylated (increasing temperature) and rehydroxylated (decreasing temperature) in the UHV analysis chamber. Plots of positive ion and negative ion ratios for all data at the various stages of hydroxylation indicated a linear relationship. Deviations from this were attributed to the presence of physisorbed water and/or surface hydrocarbon contamination.