The shells of molluscs are composed mainly of calcium carbonate crystals, with small amounts of matrix proteins. For more than 50 years, they have attracted attention for their unique mechanical and biological properties. Only recently, however, have researchers begun to realize that it is the matrix proteins that control the formation of calcium carbonate crystals and play key roles in their extraordinary properties, despite the fact that matrix proteins comprise less than 5% of the shell weight. This article reviews the matrix proteins identified to date from the shells of molluscs, their structural characteristics, and their roles in shell formation. Some suggestions are given for further investigation based on the summary and analysis.