This paper reports the results of crystallography and crystal chemistry investigation of the (Ba1−xSrx)Y2CuO5 (“green phase”) solid solution series by X-ray powder diffraction (XPD) and neutron powder diffraction techniques. The single phase regions for (Ba1−xSrx)Y2CuO5 were determined to be 0⩽x⩽0.3 for samples prepared at 810 °C in 100 Pa pO2, and 0⩽x⩽0.7 for samples prepared at 930 °C in air. All single phase (Ba1−xSrx)Y2CuO5 samples are isostructural to BaY2CuO5 and can be indexed using an orthorhombic cell with the space group Pnma. Lattice parameters, a,b,c and the cell volume, V, of the (Ba1−xSrx)Y2CuO5 members decrease linearly with increasing Sr substitution (x) on the Ba site. The general structure of (Ba1−xSrx)Y2CuO5 can be considered as having a three-dimensional interconnected network of [YO7],[(Ba,Sr)O11], and [CuO5] polyhedra. The copper ions are located inside distorted [CuO5] “square” pyramids. These pyramids are connected by the [Y2O11] groups that are formed from two monocapped [YO7] trigonal prisms sharing a triangular face. The Ba2+ ions are found to reside in distorted 11-fold coordinated cages. The oxygen sites are essentially fully occupied. XPD reference patterns of two members of the series, (Ba0.3Sr0.7)Y2CuO5 and (Ba0.7Sr0.3)Y2CuO5, were prepared for inclusion in the powder diffraction file.