•We identified sixteen arsenolipids in cod-liver oil.•Among the arsenolipids identified nine of them have not been reported before.•The degradation products of arsenolipids were also identified.•These results are essential in toxicological assessment and in epidemiologic studies of arsenic.Oils from marine samples are known to contain high concentrations of arsenolipids. However, their identification in lipid matrix poses a significant challenge especially when present in low concentrations. Here, we report the identification of sixteen arsenolipids in cod-liver oil. The fish oil was fractionated on a silica gel column and the fraction enriched with arsenic analysed using RP-HPLC online with ICP-MS and ES-Orbitrap-MS. Among the arsenolipids identified nine compounds have not been reported before. Structural assignment was achieved by arsenic signal from ICP-MS, retention time behaviour and accurate mass determination of fragment and molecular peaks. In addition, the unknown degradation products of arsenolipids eluting in the void volume were investigated using fraction collection, cation exchange chromatography and accurate mass determination, and were found to contain predominantly dimethylarsinic acid (DMA) with trace amounts of methylarsonic acid (MA), dimethylarsenopropanoic acid (DMAP) and dimethylarsenobutanoic acid (DMAB). This finding is essential in epidemiologic studies where urinary DMA and other arsenic metabolites have been used as biomarker in accessing human exposure to arsenic.