Two extended Preyssler P5W30 polyoxometalate-based inorganic-organic hybrid materials exhibiting anion-induced supramolecular isomerism were reported. Because of the cis-trans isomerism in the octahedral CoN2O4 coordination geometry, the Preyssler P5W30 polyoxometalates are extended by double O-Co-O bridges in 1α and a single O-Co-O bridge in 1β to form the isomeric 2D 4-connected 4(4)-sql and 3D 8-connected bcu networks, respectively. Both compounds show electrocatalytic abilities on the reduction of H2O2.