We report a highly efficient and chemoselective Minisci-type alkylation reaction of N-heteroarenes with alkanes under the reagent control of a hypervalent iodine oxidant PFBI-OH. In addition to the high reactivity, PFBI-OH demonstrated high steric sensitivity for H abstrac-tion of alkanes. This reaction is selective for more sterically accessible secondary C-H bonds over weaker tertiary C-H bonds. High selectiv-ity toward penultimate methylene groups was observed for a wide range of acyclic alkanes.