The effect of Bi substitution has been investigated in the palmierite type system Sr3V2O8, wherein, a new solid solution Sr3-xBi2x/3V2O8 (0 ≤ x ≤ 0.4) has been established. The structure of the composition x = 0.20 (Sr 2.8Bi0.13V2O8) was solved using single-crystal X-ray diffraction (XRD) technique. The compound crystallizes in the trigonal crystal system R3m with a palmierite structural type with a = 5.6067(4) Å, c = 20.0099(13) Å, V = 580.64(5) Å3 and Z = 3. The substituent Bi occupies a new unique 18h site resulting in a new series in palmierite class of compounds. The new solid solution has been characterized by synchrotron X-ray powder diffraction, solid-state UV-Vis diffuse-reflectance spectra, scanning electron microscopy and ionic conductivities and photocatalytic activities has been investigated. The solid solution compounds exhibited photocatalytic activity towards various classes of anionic dyes under UV radiation. © 2012 The Royal Society of Chemistry.