Spectroscopic imaging of water at the substrate / polymer interface was demonstrated by a new experimental set-up based on FTIR-ATR focal plane array (FPA) imaging and simultaneous electrochemical impedance spectroscopy measurements. The local distribution of water at the substrate / polymer interfacial region could be imaged with a lateral resolution in the micrometer range. The kinetics of local water uptake vs exposure time on polymer coated Ge as well as on polymer coated and NaCl pre-contaminated Ge surfaces was obtained. The set-up can also be used to study interfacial processes at polymer coated thin film metallic or metal oxide surfaces.