Many biologically and Fischer-Tropsch synthesized fuels contain branched alkanes which, during their combustion and atmospheric oxidation mechanism, produce methylalkyl radicals. As a result, an accurate description of the chemistry of these species is essential to integrating these fuels into our energy systems. Even though branched alkanes make up roughly one-third of the compounds in gasoline and diesel fuels, both experimental and theoretical data on methylalkyl radicals and their reactions are scarce, especially for larger chain systems and combustion conditions. The present work investigates all the hydrogen migration reactions available to the n-methylprop-1-yl through n-methylhept-1-yl radicals, for n = 2-6, using the CBS-Q G2, and G4 composite computational methods, over a wide temperature range. The resulting thermodynamic and kinetic parameters are used to determine the effect that the presence of the methyl group has on these important unimolecular, chain branching reactions, for the reactions involving not only a tertiary abstraction site but also all the primary and secondary sites. The activation energies of hydrogen migration reactions with the methyl group, either within or immediately outside the ring, are found to be roughly 0.8-1.6 kcal mol(-1) lower in energy than expected on the basis of analogous reactions in n-alkyl radicals. An important implication of this result is that the current method of using rate parameters derived from n-alkyl radicals to predict the chain branching characteristics of methylated alkyl radicals significantly underpredicts the importance of these reactions in atmospheric and combustion processes. Discussion of a possible cause for this phenomenon and its effect on the overall combustion mechanism of branched hydrocarbons is presented. Of particular concern is that 2,2,4,4,6,8,8-heptamethylnonane, which is currently used to model branched alkanes in diesel fuel surrogates, is predicted to have a much lower activation energy, by as much as 3 kcal mol(-1), for the dominant, 1,5 H-migration reactions than for the same reaction in many of the less branched alkanes that it is meant to represent. Also, counter to the currently accepted theory, the 3-methylalk-1-yl radical 1,4 and 1,5 H-migrations involving the movement of a secondary hydrogen are found to have higher rate coefficients than the corresponding reactions involving a tertiary hydrogen. The results presented here have significant implications for future experimental, computational, and combustion modeling studies.