Abstract Creating and manipulating multiple charge states of solitary defects in semiconductors is of essential importance for solitary defect electronics, but is fundamentally limited by Coulomb's law. Achieving this objective is challenging, due to the conflicting requirements of the localization necessary for the sizable band gap and delocalization necessary for a low charging energy. Here, using scanning tunneling microscopy/spectroscopy experiments and first-principles calculations, we realized exotic quinary charge states of solitary defects in two-dimensional intermetallic semiconductor Sn2Bi. We also observed an ultralow defect charging energy that increases sublinearly with charge number rather than displaying the usual quadratic behavior. Our work suggests a promising route for constructing multiple defect-charge states by designing intermetallic semiconductors, and opens new opportunities for developing quantum devices with charge-based quantum states.