RbFeO(2), rubidium oxoferrate, crystallizes as an orthorhombic structure. The crystals under investigation were composed of six individuals representing reticular pseudomerohedral twins with a pseudocubic twin lattice of index 4 because of the approximate equations a(8)(1/2) = b(2)(1/2) = c. The compound is isostructural with KFeO(2) (KGaO(2) type of structure) and is composed of [FeO(4/2)](-) corner-sharing tetrahedra, forming a three-dimensional cristobalite-like network, with Rb(+) ions occupying its interstices.