The photochemical and photophysical behaviour of metal complexes remains a primary reason for the continuing and increasing interest in their study by both established and more recently developed spectroscopic techniques. The diversity of spectroscopic properties arises in large part from population of the wide range of electronic states accessible to mono-and multi-nuclear metal-centred species, including biomimetic model systems, as well as metalloproteins. Detailed investigation of the vibrational and vibronic energy states under both static and timeresolved conditions is especially important in the development of a more complete understanding of the structure and dynamics of these systems. In many cases these studies focus on their role in biological function and potential application in catalytic and photocatalytic contexts. This report selects a number of recent examples of the use of Raman and resonance Raman methods to probe a variety of metal-centred systems ranging from biomimetic oxidation catalysts to spin-crossover complexes. In addition, the application of techniques developed more recently such as femtosecond stimulated Raman scattering, femtosecond coherence spectroscopy and timeresolved X-ray absorption spectroscopy will be discussed.