The carbonylation of dimethyl ether (DME) with carbon monoxide on Rh-promoted cesium salt of 12-tungstophosphoric acid, Rh/Cs2HPW12O40 (HPA), has been studied with C-13 solid-state NMR. The bifunctional character of Rh/Cs2HPW12O40 catalyst in halide-free carbonylation of DME has been directly demonstrated. The activation of the C-O bond of DME proceeds on Bronsted acid sites of HPA with the formation of the methyl group attached to the surface of HPA (methoxy species), whereas the role of rhodium consists in trapping carbon monoxide from gaseous phase and a transfer of CO to the center of DME activation, acidic OH-group of the catalyst, in the form of rhodium carbonyls. The lattice of Cs2HPW12O40 makes it possible to locate these two different active centers in close proximity to each other, e.g., on two adjacent oxygen atoms, terminal and bridging, of one Keggin anion, thus facilitating the insertion of carbon monoxide from rhodium carbonyl into the C-O bond of methoxy-group to produce the acetate group bound to the Keggin anion. The latter offers finally methyl acetate under the interaction with DME, the intermediate surface methoxy-groups being restored. (C) 2010 Elsevier Inc. All rights reserved.