Improving the performance and lowering the analyte detection limits of optical and electronic biosensors is essential for advancing wide ranging applications in diagnostics and drug discovery. Most sensing methods require direct linkage of a recognition element and a sensor, which is commonly accomplished through an organic monolayer interface. Alkoxyorganosilanes are typically used to prepare sensor surfaces on dielectric oxides. However, many silanes lead to roughened or thick interfaces that degrade device sensitivity. Here, controlled vapor phase deposition of monoalkoxysilanes is found to lead to monolayers resistant to elevated temperatures and extreme pH conditions. The formation of high density, subnanometer monolayers is demonstrated by ellipsometry, XPS, and AFM. The uniform attachment of these monofunctional silanes to such biosensing platforms as microarrays, field effect devices, and the formation of surface enhanced Raman spectroscopy substrates is demonstrated. The advantages of using this silane deposition protocol for the above technologies are also discussed.