Hydrogen plasmas have been used to etch surfaces of semiconducting materials (e.g., GaAs, GaSb, InP, Si), their oxides, and Si nitride. Using a combination of analytical techniques—spectroscopic ellipsometry, Auger spectroscopy, and scanning electron microscopy (SEM), the etch rates, the surface composition and morphology have been studied. It is demonstrated that the selective etching rate of hydrogen plasma for Si over SiO2 is ∠30, and that for GaAs oxide over GaAs is ∠2. It is also shown that the hydrogen plasma etched (and air exposed) GaAs surfaces have a Ga/As concentration ratio nearly equal to that of the air cleaved GaAs surface. Similar results have also been obtained for GaSb. Hydrogen plasma etched InP shows surface segregation and is rich in In. The etch rates of the semiconductors and their oxides vary by several orders of magnitude from compound to compound as determined from ellipsometry and SEM. It is also demonstrated that scanning ellipsometry can be used to monitor surface etching processes. Some advantages and disadvantages of the use of hydrogen plasma for surface preparation and etching applications are discussed.