An overview of the strategies applied for the collection of X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine-structure (EXAFS) measurements in combination with UV–visible and vibrational spectroscopy is developed in the context of the sampling requirements of the relevant techniques. Case studies highlight cases in which the sample is homogeneous but undergoing reaction, inhomogeneous and the short-lived products of chemical reactions. Sampling approaches which use optical fibres or attenuated total reflection allow coincident measurement of the X-ray and complementary spectroscopic measurements and this is complemented by strategies which allow the study of spectroscopy-validated, freeze-quenched ex situ samples.