© 2015 Georg Thieme Verlag Stuttgart, New York-Synlett. Recent developments in the Markovnikov-selective hydrofunctionalization of unactivated olefins are presented. Our group found that the use of a cobalt complex, an N-fluoropyridinium salt, and a siloxane facilitates hydrofunctionalization with excellent functional group tolerance. Mechanistically, this catalysis involves both a carbon radical and a carbocationic intermediate.