Once the periodic properties of elements were unveiled, chemical behaviour could be understood in terms of the valence of atoms. Ideally, this rationale would extend to quantum dots, and quantum computation could be performed by merely controlling the outer-shell electrons of dot-based qubits. Imperfections in semiconductor materials disrupt this analogy, so real devices seldom display a systematic many-electron arrangement. We demonstrate here an electrostatically confined quantum dot that reveals a well defined shell structure. We observe four shells (31 electrons) with multiplicities given by spin and valley degrees of freedom. Various fillings containing a single valence electron—namely 1, 5, 13 and 25 electrons—are found to be potentia...