Strain and stress at the Si surface have been studied by photoreflectance (PR) spectroscopy. A Si diaphragm structure has been fabricated in order to produce the surface strain caused by N-2 gas pressure which changes the PR spectra of the Si diaphragm. The transition energy obtained from the PR peak energy of approximately 3.4 eV is proportional to the surface stress, which is calculated by elastic analysis. Additionally, PR spectroscopy was applied to measure stress at the interface between the Si and thermal oxide. As the SiO2 growth temperature increases, the interface stress decreases. From our experimental results, it is considered that PR spectroscopy is effective as a contactless and nondestructive monitoring technique for Si surface stress.