The title compound, [(S)-C6H5C2H4NH3][PbBr3], crystallizes as an organic–inorganic hybrid. As such, the structure consists of extended chains of [PbBr3]− units running along the a axis. Each Pb atom is octahedrally coordinated by six bromides, arranged as chains of face-sharing octahedra. These inorganic chains are separated by the isolated organic cations.