To investigate the chemical changes occurring at metal/lubricant interfaces under tribological conditions in the boundary-lubrication regime, an in situ system for conducting quantitative tribological measurements has been constructed by combining an attenuated total reflection Fourier-transform infrared (ATR/FT-IR) spectrometer with a reciprocating tribometer. By periodically acquiring ATR/FT-IR spectra during sliding, spectroscopic changes due to thermal and/or tribochemical reactions occurring at the metal/oil interface can be monitored and correlated with friction measurements. The usefulness of this tribological test system has been demonstrated by performing ATR tribological experiments in the presence of a poly-α-olefin base oil at high temperature (423 K) on iron-coated germanium ATR crystals.