Nuclear magnetic resonance, mid and near infrared, and ultra violet (UV) spectra of wood contain information on its chemistry and composition. When solid wood samples are analysed, information on the molecular structure of the lignocellulose complex of wood e.g. crystallinity of polysaccharides and the orientation of the polymers in wood cell walls can also be gained. UV and infrared spectroscopy allow also for spatially resolved spectroscopy, and state-of-the-art mapping and imaging systems have been able to provide local information on wood chemistry and structure at the level of wood cells (with IR) or cell wall layers (with UV). During the last decades, these methods have also proven useful to follow alterations of the composition, chemistry and physics of the substrate wood after fungi had grown on it as well as changes of the interactions between the wood polymers within the lignocellulose complex caused by decay fungi. This review provides an overview on how molecular spectroscopic methods could contribute to understand these degradation processes and were able to characterise and localise fungal wood decay in its various stages starting from the incipient and early ones even if the major share of research focussed on advanced decay. Practical issues such as requirements in terms of sample preparation and sample form and present examples of optimised data analysis will also be addressed to be able to detect and characterise the generally highly variable microbial degradation processes within their highly variable substrate wood.