We show that cobalt bis(acetylacetonate) [Co(acac)₂], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et₃SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)₂–TBHP–Et₃SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings.