Alkane functionalization with carbon-electrophiles remains virtually unexplored under thermo-driven hydrogen atom transfer (HAT) conditions due to a challenge of integrating oxidation and reduction in a single operation. We report here a Ni-catalyzed arylation and alkylation of alkane C‒H bonds with organohalides to forge C(sp3)‒C bonds by merging easily accessible Zn and tBuOOtBu (DTBP) as the external reductant and oxidant. The mild and easy-to-operate protocol enables facile carbofunctionalization of N-/O-α- and cyclohexane CH bonds, and preparation of a number of bioactive compounds and drug derivatives. Preliminary mechanistic studies implied a Ni(I)-mediated DTBP reduction followed by alkane HAT to tBuO radical. The marked compatibility of Zn and DTBP with nickel-catalysis may invoke the development of external oxidant and reductant co-trigged thermoredox bond forming approaches based upon challenging substrates.