Palladium catalyzed Suzuki, Heck and Sonogashira coupling reactions were studied as reaction protocols for organic modification of Si surfaces. These synthetically useful protocols allow for surface modification of alkene, alkyne and halide terminated surfaces. Surface oxidation and metal contamination was assessed by X-ray photoelectron spectroscopy. The nature of the primary passivation layer was an important factor in the oxidation resistance of the Si surface during the secondary functionalization. Specifically, the use of alkynes as the primary functionalization layer gave superior stability compared to alkene analogues. The ability to utilize Pd catalyzed coupling chemistries on Si surfaces opens great versatility for potential molecular and nanoscale electronics and sensing/biosensing applications.