Single crystals of α-Ba(2)P(2)O(7), dibarium diphosphate, were obtained by solid-state reaction. The ortho-rhom-bic structure is isotypic with α-Sr(2)P(2)O(7) and is the second polymorph obtained for this composition. The structure is built from two different BaO(9) 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 [010] and either edges or triangular faces perpendicularly to [010] to form the three-dimensional framework. This polyhedral linkage delimits large channels parallel to [010] where the P(2)O(7) 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 BaO(9) polyhedra through edges and corners.