In an effort to elucidate their structures, mass-selected Cl-−(CH4)n (n = 1−10) clusters are probed using infrared spectroscopy in the CH stretch region (2800−3100 cm-1). Accompanying ab initio calculations at the MP2/6-311++G(2df,2p) level for the n = 1−3 clusters suggest that methane molecules prefer to attach to the chloride anion by single linear H-bonds and sit adjacent to one another. These conclusions are supported by the agreement between experimental and calculated vibrational band frequencies and intensities. Infrared spectra in the CH stretch region for Cl-−(CH4)n clusters containing up to ten CH4 ligands are remarkably simple, each being dominated by a single narrow peak associated with stretching motion of hydrogen-bonded CH groups. The observations are consistent with cluster structures in which at least ten equivalent methane molecules can be accommodated in the first solvation shell about a chloride anion.