The synthesis and structure of the isostructural acentric compounds Sr3Be2B5O12(OH) (1) and Ba3Be2B5O12(OH) (2) are reported for the first time. These compounds crystallize in the space group R3m, and the unit cell parameters are a = 10.277(15) angstrom and c = 8.484(17) angstrom for land a = 10.5615(15) angstrom and c = 8.8574(18) angstrom for 2. The structures consist of a network of [Be2B4O12(OH)] units interwoven with a network consisting of MO9 polyhedra (M = Sr, Ba) and BO3 triangles and exemplify how acentric building blocks such as [BO3](3-), [BO4](5-), and [BeO4](6-) can be especially suitable to build noncentrosymmetric long-range structures. Both networks are centered on the 3-fold rotation axis and present themselves in alternating fashion along [001]. Acentricity is imparted by the alignment of the polarities of BO3 and BeO4 environments. Infrared spectroscopy has been used to confirm the local geometries of B and Be, as well as the presence of hydroxide in the crystal structure. Another interesting feature of these compounds is the presence of disorder involving Be and B at the tetrahedral Be site. The degree of the disorder has been confirmed by observing a noticeable shortening of average Be-O bond distances.