Nanoscaled noble metals exhibit unique optical properties. One of these is the ability to create localised surface plasmon resonances upon light illumination, which makes it possible to study adsorbed molecules via surface enhanced spectroscopy. Silver and gold nanostructured electrodes with plasmonic properties can be created via electrochemical roughening or electro deposition methods. For studying enzyme/electrode systems the metal surface has to be functionalised with a biocompatible surface layer. Once the electrode is incorporated in an electrochemical cell the system can be studied by spectroelectrochemistry. With this combinational approach catalytic efficiency can be tested via electrochemistry while the structural state of the enzyme is probed via surface enhanced Raman spectroscopy. Several techniques will be presented in this book chapter to create plasmonic electrode systems via electrochemical methods with defined optical and chemical properties. A focus will be given on the formation of hybrid electrode systems that make it possible to study enzyme/electrode interactions also on non plasmonic interfaces. Furthermore spectroelectrochemical investigations on several enzyme/electrode systems are discussed. It is shown how the combination of electrochemistry with spectroscopy can be used to get mechanistic insight into the functionality of enzymes on surfaces. This information can then be used for rational design of biosensors and biofuel cells.