2,6‐Disubstituted iodoarenes bearing amide‐functionalized side arms are reported as new structures in redox‐active iodine(I/III) catalysis. In combination with bis‐sulfonimides as nitrogen sources and 3‐chloroperbenzoic acid (mCPBA) as benign terminal oxidant they catalyze the vicinal diamination of styrenes. The obtained reactivity and selectivity outperform other iodoarene catalyst candidates. This protocol provides a sustainable alternative to previous related protocols for diamination that are based on stoichiometric iodine(III) reagents.