A new gold standard: Phosphaphenalene gold(I) complexes are potent anticancer drugs. Subtle structural modifications of the phosphaphenalene core lead to remarkable photophysical properties and enhance the activity of the gold complexes against cancer. In particular, pyrrole‐based phosphaphenalene derivatives exhibit high efficacy towards 14 different brain cancer cell lines including glioblastomas, brain metastases, meningiomas, IDH‐mutant gliomas and head and neck cancers, reaching IC50 values of as low as 730 nM. Moreover, the photophysical properties of the phosphaphenalenes introduce the possibility to develop theranostic applications. More information can be found in the Research Article by C. Herold‐Mende, C. Romero‐Nieto, et al. (DOI: 10.1002/chem.202104535).