A functional group tolerant cobalt-catalyzed method for the intermolecular hydrofunctionalization of alkenes with oxygen- and nitrogen-based nucleophiles is reported. This protocol features a strategic use of hypervalent iodine(III) reagents that enables a mechanistic shift from conventional cobalt-hydride catalysis. Key evidence was found supporting a unique bimetallic-mediated rate-limiting step involving two distinct cobalt(III) species, from which a new carbon-heteroatom bond is formed.