Reactions of non-lacunary Keggin ([PW 12 O 40 ] 3− ) and Dawson ([α-P 2 W 18 O 62 ] 6− ) polyoxometalates with rhodium (II) acetate have been studied. In the first case reaction yields the layered coordination polymer Li 3 [(Rh 2 (CH 3 COO) 4 ) 2 (PW 12 O 40 )]·12.5 H 2 O (1), where polyoxoanions are coordinated via oxygen atoms to the {Rh 2 } 4+ core. In the case of [α-P 2 W 18 O 62 ] 6− dirhodium clusters do not coordinate the polyoxoanion directly; however, they form K 7 [P 2 W 18 O 62 ][Rh 2 (CH 3 COO) 4 X]·nH 2 O, where X=Cl, n=11.37 (2); Br, n=11.1 (3), which contain polymeric chain polyanions catena-[Rh 2 (CH 3 COO) 4 X] n n − (X=Cl, Br). Coordination polymer 1 is active in total oxidation of hydrogen and olefin at relatively low temperatures.