Clusters formed between a fluoride anion and several hydrogen sulfide molecules have been investigated via ab initio calculations at the MP2 level of theory, using Dunning’s augmented correlation consistent basis sets. Optimised geometries, vibrational frequencies, and enthalpy changes for the ligand association reactions are presented for clusters with up to five H2S ligands interacting with a F− anion. The minimum energy structure for the 1 : 1 F−-H2S complex features proton transfer from the H2S to the F− anion, forming a planar Cs symmetry FHSH− structure. For the F−–(H2S)2 cluster, the FHSH− core remains and is solvated by a perturbed H2S ligand. For the larger F−–(H2S)3–5 clusters, in addition to the FHSH−–(H2S)n cluster forms, other minima featuring a ‘solvated F−’ anion are predicted. Calculated infrared spectra for the minima of each cluster size are presented to aid in assigning spectra from future experimental studies.