Molecular structures, in chloroform and DMSO solution, of the monounsaturated free fatty acids (FFAs) caproleic acid (dec-9-enoic acid) and oleic acid (octadec-9-enoic acid) and the ω-3 FFAs α-linolenic acid (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid ALA), eicosapentanoic acid (5Z,8Z,11Z,14Z,17Z)-icosa-5,8,11,14,17-pentaenoic acid) and docosahexaenoic acid (4Z,7Z,10Z,13Z,16Z,19Z)-docosa-4,7,10,13,16,19-hexaenoic acid), are reported with the combined use of NMR and DFT calculations. Variable temperature and concentration chemical shifts of the COOH protons and transient 1D NOE experiments, in CDCl3, demonstrate the major contribution of low molecular weight aggregates of dimerized fatty acids, through intermolecular hydrogen bond interactions of the carboxylic groups, with parallel and antiparallel interdigitated structures, even at the low concentration of 20 mM. For the dimeric DHA, a structural model of an intermolecular hydrogen bond through carboxylic groups and an intermolecular hydrogen bond between the carboxylic group of one molecule and the ω-3 double bond of a second molecule, is shown to play a role. In DMSO-d6 solution the centro-symmetric hydrogen bond interactions are broken and the carboxylic groups form strong intermolecular hydrogen bond interactions with a discrete solvation molecule of DMSO. These solvation species form parallel and antiparallel interdigitated structures of low molecular weight. DFT structural models in CHCl3 and DMSO, in agreement with the NMR data, are compared with the structures in the liquid state