The initial acquisition of calcium carbonate polymorphs (aragonite and calcite) at the onset of skeletal biomineralization by disparate metazoans across the Ediacaran-Cambrian transition is thought to be directly influenced by Earth's seawater chemistry. It has been presumed that animal clades that first acquired mineralized skeletons during the so-called “aragonite sea” of the latest Ediacaran and earliest Cambrian (Terreneuvian) possessed aragonite or high-Mg calcite skeletons, while clades that arose in the subsequent “calcite sea” of Cambrian Series 2 acquired low-Mg calcite skeletons. Here, contrary to previous expectations, we document shells of one of the earliest helcionelloid molluscs from the basal Cambrian of southwestern Mongolia that are composed entirely of low-Mg calcite and formed during the Terreneuvian aragonite sea. The extraordinarily well-preserved Postacanthella shells have a simple prismatic microstructure identical to that of their modern low-Mg calcite molluscan relatives. High-resolution scanning electron microscope observations show that calcitic crystallites were originally encased within an intra- and interprismatic organic matrix scaffold preserved by aggregates of apatite during early diagenesis. This indicates that not all molluscan taxa during the early Cambrian produced aragonitic shells, weakening the direct link between carbonate skeletal mineralogy and ambient seawater chemistry during the early evolution of the phylum. Rather, our study suggests that skeletal mineralogy in Postacanthella was biologically controlled, possibly exerted by the associated prismatic organic matrix. The presence of calcite or aragonite mineralogy in different early Cambrian molluscan taxa indicates that the construction of calcium carbonate polymorphs at the time when skeletons first emerged may have been species dependent.