Abstract: Pojetaia and Fordilla are the oldest bivalve molluscs, occurring in roughly co-eval rocks from the Tommotian, and are the only undisputed, well-known bivalves from the Cambrian. New specimens reveal that Pojetaia had a laminar inner shell microstructure reminiscent of the foliated aragonite of modern monoplacophorans, and the same is true for Fordilla. A similar shell microstructure is seen in Anabarella and Watsonella, providing support for the hypothesis that they are the ancestors of bivalves. Foliated aragonite shares many similarities with nacre, and it may have been the precursor to nacre in bivalves. No cases of undisputed nacre occur in the Cambrian, in spite of much shell microstructure data from molluscs of this time period. Thus, although considered by many to be homologous among molluscs, we conclude that nacre convergently evolved in monoplacophorans, gastropods, bivalves, and cephalopods. This independent origin of nacre appears to have taken place during, or just prior to, the Great Ordovician Biodiversification Event and represents a significant step in the arms race between predators and molluscan prey.