The potential access to Co IV species for promoting transformations that are particularly challenging at Co III still remains underexploited in the context of Cp*Co‐catalyzed C–H functionalization reactions. Herein, we disclose a combined experimental and computational strategy for uncovering the intermediacy of Cp*Co IV species in a Cp*Co‐mediated C–S bond‐reductive elimination. These studies support the intermediacy of high‐valent Cp*Co intermediates in C–H functionalization reactions, under oxidative conditions, when involving nucleophilic coupling partners.