The hydroxylation and dehydroxylation behavior of amorphous silica fracture surfaces was studied using temperature-programmed static SIMS. The results show that vacuum heat treatments result in more extensive condensation of silanol groups on the silica glass fracture surface as compared to fumed silica (Cabosil). This is attributed to differences in the distribution of silanol groups on the two silica surfaces. The rehydration kinetics of the dehydroxylated silica fracture surfaces showed two distinct reaction rates-an initial rapid increase in the silanol concentration, followed by a slower rehydration for longer dosing times. The slower rehydration reaction was shown to follow first-order reaction kinetics with the reaction rate constant, suggesting hydrolysis of strained siloxane bonds on three-membered silicate ring structures. The much faster initial rehydration is attributed to the hydrolysis of extremely strained siloxane bonds in two-membered, edge-shared tetrahedral rings. The effect of the dehydration time and temperature (i.e., thermal history of the surface) on the rehydration kinetics is also discussed.