The EPR spectra of n-alkyl, 2-methylalkyl, 2,2-dimethylalkyl, 2,2,3-trimethylbutyl, and 2,2,3,3-tetramethylbutyl radicals indicate that at 90 K they exist in "rigid" conformations with respect to rotation about the Cβ-Cγ bonds. The preferred conformations about the Cα-Cβ and Cβ-Cγ bonds were deduced by analysis of the β- and γ-H hyperfine splittings (hfs). 2,2,3,3-Tetramethylbutyl radicals, the only radicals with a CH3 group approximately all-trans with respect to the semioecupied p-orbital, were also the only radicals to show resolved δ-hfs. The barriers to internal rotation of the methyl groups in n-propyl, isobutyl, neopentyl, 2,2-bis(trideuteriomethyl)butyl, and 2,2,3,3-tetramethylbutyl radicals were obtained by line shape analysis; the ethyl rotation barrier in 2,2-bis(trideuteriomethyl)butyl and the tert-butyl rotation barrier in 2,2,3,3-tetramethylbutyl radicals were estimated in a similar way. The experimental hfs of trans γ-hydrogens were shown to fit a relationship of the form aHγt = 0.1 + 7.9 cos2 Φ, where Φ is the dihedral angle between the SOMO and the plane through Cα, Cβ, and Cγ. Trends in the internal rotation barriers of the alkyl groups were adequately accounted for in terms of steric effects.