We explored the reactivity of gold on cleaved 2212 BiCaSrCuO by synchrotron‐radiation photoemission spectroscopy. We found no evidence for reactivity when the substrate was at room temperature, similar to what has been reported for very low temperatures (20 K). At intermediate temperatures (100 K), however, clear evidence was found of a chemical reaction with formation of a localized nonmetallic phase. These findings have potentially important implications for the manufacturing of devices based on BiCaSrCuO.