Single crystals of α-Ba2P2O7, dibarium diphosphate, were obtained by solid-state reaction. The orthorhombic structure is isotypic with α-Sr2P2O7 and is the second polymorph obtained for this composition. The structure is built from two different BaO9 polyhedra (both with m symmetry), with Ba—O distances in the ranges 2.7585 (10)–3.0850 (6) and 2.5794 (13)–2.9313 (4) Å. These polyhedra are further linked by sharing corners along  and either edges or triangular faces perpendicularly to  to form the three-dimensional framework. This polyhedral linkage delimits large channels parallel to  where the P2O7 diphosphate anions are located. These groups (symmetry m) are characterized by a P—O—P angle of 131.52 (9)° and an eclipsed conformation. They are connected to the BaO9 polyhedra through edges and corners.