Over the years, molluscan shells have become an exemplar model system to study the process of mineral formation by living organisms, the process of biomineralization. Typically, the shells consist of a number of mineralized ultrastructural motifs, each exhibiting a specific mineral-organic composite architecture. These are made of calcium carbonate building blocks having a well-defined three-dimensional morphology that is significantly different from the shape of inorganically formed counterparts. Shell ultrastructures are known to form via a biologically controlled extracellular mineralization pathway in which the organism has no direct control over mineral formation. The cellular tissue, responsible for shell biomineralization, forms an organic framework and sets-up the physical conditions necessary for the deposition of a specific morphology, whereas the growth of the mineral part of the shell proceeds spontaneously via the process of self-assembly. In this feature article, the ability to employ thermodynamic models from classical materials science to describe the process of self-assembly and structural evolution of a variety of shell architectures is reviewed. Having the potential to offer an analytical framework to express ultrastructure formation in time and in space, these models not only provide a deeper insight into shell biomineralization, but also suggest tools for novel composite materials design.