We propose a novel heterostructure system consisting of compounds with chemical formula A(2)Mo(3)O(8) (A, B: Zn, Mg, Cd) that can host a two-dimensional electron/hole gas (2DEG/2DHG). The formation of a 2DEG/2DHG in these heterostructures, which have a low interfacial strain, is driven by a polarization discontinuity at the interface. The sheet carrier densities and charge localization in these heterostructures are comparable to other well-known heterostructures that host 2DEG opening up the possibility of a wide variety of applications. Published under license by AIP Publishing.