An in-depth understanding of internal relation barrier formation and energetics for dimethyl ether, protonated dimethyl ether, methanol, and their sulfur analogs is provided by dissecting the barrier into Pauli exchange steric repulsion, sigma-lone-pair reorganization, and pi hyperconjugation. The combined natural bond orbital, symmetry, and relaxation analysis demonstrates that oxygen sigma lone-pairs play an important (sometimes dominant) role in controlling barrier heights. in dimethyl ether the increased steric contact brought about by simultaneous relation of the methyl groups causes the COC angle to widen, in turn increasing the sigma lone-pair p character, which leads to large lone-pair reorganization energy. Steric repulsion contributes to the dimethyl ether >4 kcal/mol barrier energy in only a minor way even though the steric contact can be looked at as the origin of the lone-pair increased p character. Absence of a sigma lone-pair in acid media predicts a drastically lowered barrier (i.e.similar to kcal/mol). In methanol the increase in O atom lone-pair p character and associated lone-pair reorganization energy is strongly reduced, leading to an also greatly lowered barrier. Lone-pair sigma reorganization effects are smaller in the sulfur-containing compounds, and C-S (sigma) bond weakening is predicted to become the dominant barrier energy controlling term.