Although the composition of chlorite groupminerals represents a known proxy for conditions in various geological environments, few comparative studies of chlorites from different geological environments have been carried out. In this study, we compare chlorites from a hydrothermal system with those formed under low-grade metamorphic conditions. Both sets of samples were collected from the Pilbara Craton,Western Australia. Near-infrared (NIR) spectroscopy was used to determine if spectral differences record compositional differences between chlorites from the two geological environments. The spectra showed a significant difference in the Mg-OH absorption wavelength, near 2350 nm, with the hydrothermal group showing longer absorption wavelengths than the metamorphic one. A comparison of the spectral data with geochemical analyses showed a relation between the absorption wavelength and the magnesium-to-iron ratio (magnesium number) of chlorite, as well as the bulk rock composition. Metamorphic rocks have a higher magnesium-to-iron ratio than the hydrothermal ones, predominantly explained by differences in the degree of metasomatism. In the hydrothermal system,mass transfer changes the bulk rock compositionwhile for themetamorphic samples the original bulk chemistry determines the current composition of the rock.