The title compound, [CrRb(C(2)O(4))(2)(H(2)O)(2)](n), obtained under hydrothermal conditions and investigated structurally at 100 K, is a three-dimensional supramolecular isomer of the layered structure compound studied at room temperature. This novel polymer is built up from crosslinked heterobimetallic units. The linkage of alternating edge- and vertex-shared RbO(7)(H(2)O)(2) and CrO(4)(H(2)O)(2) polyhedra running along three different directions gives a dense packing. The two independent ligands display two η(4)-chelation modes and two conventional carboxylate bridges. However, the pentadentate ligand connects the Cr(III) and Rb(I) ions through one O-atom bridge, while the hexadentate ligand exhibits an additional η(3)-chelation and two O-atom bridges. Each coordinated water molecule forms an O-atom bridge between the two metals. Moreover, in the absence of protonated ligands, these water molecules act as donors through their four H atoms in strong-to-weak hydrogen bonds. This results in zigzag chains of alternating oxalate and aqua ligands parallel to the twofold screw axis. The six double oxalates known to date containing an alkali and Cr(III) all present layered two-dimensional structures. In the series, this supramolecular isomer is the first three-dimensional framework.