Conotoxins are peptides isolated from the venom of cone snails, which remain of significant interest in drug design and the development of pharmacological tools. The conotoxin family is extensive with 32 different cysteine frameworks, 30 gene superfamilies and thousands of mature toxin sequences have been identified. Conotoxins have been shown to selectively and potently target a range of ion channels and receptors, including sodium and calcium channels and nicotinic acetylcholine receptors. Structural analyses have been critical in developing conotoxins as drug leads and pharmacological tools and although more than 200 conotoxin structures have been determined, there are thousands of conotoxins yet to be fully characterised. We have used NMR spectroscopy to study the structures of native conotoxins isolated from milked venom and our structural studies have highlighted a new structural motif in the conotoxin family.