Dimethylsilanediol is a stable crystalline solid that was described in 1953. As the monomer of an important class of commercial products (poly(dimethylsiloxanes)-silicones, PDMS) and as a simple molecule in its own right (the silicon analog of acetone hydrate), it has been neglected by several fields of fundamental and applied research including the hydrophobization of inorganic oxide surfaces. We report that dimethylsilanediol is a useful reagent for the surface modification (hydrophobization) of oxidized silicon and other oxidized metal surfaces and compare the wetting properties of modified solids with those of conventionally modified surfaces. That water is the only byproduct of this modification reaction suggests that this and likely other silanediols are useful surface-modification agents, particularly when substrate corrosion or the competitive adsorption of byproducts is an issue. We note that dimethylsilanediol is volatile with a significant vapor pressure at room temperature. Vapor-phase surface modifications are also reported.