Anode activity in high current vacuum arcs leads to the formation of various high current modes and transitions between them. Intense material evaporation during the anode spot mode and formation of a neutral vapour cloud during the anode plume mode modify the arc plasma properties and, hence, can have a crucial impact in applications, like e.g. reduction of interruption performance of switching devices. The influence of anode mode appearance on arc plasma parameters and on anode surface temperature was studied in detail by a novel optical diagnostic technique—intensified video optical emission spectroscopy. Employing advanced diagnostic methods, the ground state density, excitation temperature and pressure profiles close to the anode surface have been determined. For the anode plume mode, higher copper vapour pressure was found in the plume shell compared to its core. The copper ion density distribution shows a maximum outside of the plume shell. Consequently, a higher electrical conductivity in the surrounding area of the plume might be expected, i.e. the arc current flows around the plume rather than through it. Analysis of the temporal evolution of electrical and optical signals reveals that voltage jumps and drops during the mode transitions are accompanied by noticeable changes in the anode surface temperature. Thus, the formation of the anode plume leads to temperature lowering while the transition to the anode spot mode is accompanied by a temperature increase. In general, a clear correlation between electrode surface temperature and arc voltage in the case of constricted anode attachment is found. The results of this study give new insights into anode plume properties and consequences of anode mode transitions. Reversible mode transitions and correlations between arc voltage and anode surface temperature, as well as changes in the current path during anode plume mode, have to be considered as factors for optimization of electrode design and choice of materials for switching applications.