Numerous transition metal-mediated reactions, including hydrogenations, hydrosilations, and alkane functionalizations, result in the cleavage of strong σ bonds. Key intermediates in these reactions often involve coordination of the σ bond of dihydrogen, silanes (Si-H), or alkanes (C-H) to the metal center without full scission of the bond. These σ complexes have been characterized to varying degrees in solid state and solution. However, a σ complex of the simplest hydrocarbon, methane, has eluded full solution characterization. Here, we report nuclear magnetic resonance spectra of a rhodium(I) σ-methane complex obtained by protonation of a rhodium-methyl precursor in CDCl2F solvent at -110°C. The σ-methane complex is shown to be more stable than the corresponding rhodium(III) methyl hydride complex. Even at -110°C, methane rapidly tumbles in the coordination sphere of rhodium, exchanging free and bound hydrogens. Kinetic studies reveal a half-life of about 83 minutes at -87°C for dissociation of methane (free energy of activation is 14.5 kilocalories per mole).