Cu I (Cu neutrals) excitation temperature is usually measured by researchers while analyzing vacuum arcs (ignited by CuCr electrodes). Since ions may have information that neutrals do not have, measuring Cu II (Cu <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{+})$</tex-math> </inline-formula> might reveal some new features of the vacuum arc. In this article, Cu II excitation temperature is measured by observing seven Cu II lines. Measurement results show the existence or not of a Cr component in a vacuum arc can greatly change the 2-D distribution pattern of Cu II excitation temperature (researchers suggest no influence on Cu I); from a “flat” shape changes to a “columnar” or a “bowl” shape (related to gap length). However, the Cr ratio in CuCr electrodes does not cause a noticeable difference both in Cu II excitation temperature value and in 2-D distribution shape. In the case of CuCr electrodes, before the arc mode change to anode spot mode, a new phenomenon occurs under diffuse mode; as the arc current grows higher than a critical value under a certain length of the gap, the temperature starts to drop in the area near the anode surface, forming a temperature valley. This temperature valley can be interpreted as a local increase in Cu II density. The local ion eruption caused by the Cr component might be a trigger or a pre-process for arc mode changing to anode spot mode.