Applicability of Fourier transform infrared (FTIR) spectroscopy to an in situ diagnostics tool of plasma–surface interactions is described. After a brief review of conventional reflection absorption spectroscopy (RAS) and phase-modulated RAS (PMRAS), our FTIR phase-modulated spectroscopic ellipsometry (PMSE) is described in detail. The FTIR PMSE is constructed by insertion of a grid polarizer as an analyser in front of an infrared detector in addition to the conventional set-up of PMRAS. This simple change brings about a higher sensitivity than that of conventional PMRAS, which enables us to detect chemical species generated on (or removed from) the top surface layer during plasma processing. This feature is demonstrated by the fact that our FTIR PMSE can be applied to surface diagnostics during reactive ion etching processes such as for Si, SiO2/Si, SiO2/Si3N4, SiO2/photo-resist and low-dielectric-constant films.