Near-infrared spectroscopy (NIR) has been used to analyse alunites of formula K(Al3+)6(SO4)4(OH)12. Whilst the spectra of the alunites shows a common pattern differences in the spectra are observed which enable the minerals to be distinguished. These differences are attributed to subtle variations in alunite composition. The NIR bands in the 6300-7000 cm(-1) region are attributed to the first fundamental overtone of both the infrared and Raman hydroxyl stretching vibrations. A set of bands are observed in the 4700-5500 cm(-1) region which are assigned to combination bands of the hydroxyl stretching and deformation vibrations. NIR spectroscopy has the ability to distinguish between the alunite minerals even when the formula of the minerals is closely related. The NIR spectroscopic technique has great potential as a mineral exploratory tool on planets and in particular Mars.