One of the remaining challenges facing state-of-the-art nickel-based SOFC anodes is their susceptibility to degradation induced by redox cycling and chemical poisoning, most notably by carbon and sulphur. An enhanced scientific understanding of chemical interactions on the surface of SOFC electrodes is therefore critical to the development of robust nickel-based anodes. This paper draws together work on advanced electrochemical studies, thin-foil samples, and Raman spectroscopy studies of anode materials, together with results from a new customized SOFC test rig using combined in situ Raman and electrochemical measurements. The in situ test rig opens up a whole range of new research possibilities and these will be discussed.