In this paper we describe the synthesis and characterization of a polystyrene-tethered Nb-complex. namely P-C6H4-p-CH2CH2-NbCl4, 1 which reacts with CH3OH to afford P-C-6-H-4-p-CH2CH2-NbCl(OCH3)(3) 2. The latter inserts CO2 to afford P-C6H4-p-CH2CH2-NbCl[O-C(O)OCH3](OCH3)(2), 3. active in the catalytic carboxylation of methanol. The insertion of only one mol CO2 per Nb has been determined both by measuring the CO2 released upon treatment with HCl and by solid state C-13 NMR. 3 is easily recovered from the reaction medium and re-used: it can also be used in a flow reactor without decomposition after days. It shows good recycling properties and is much easier to use than the relevant homogeneous catalyst Nb(OCH3)(4)[O-C(O)OCH3]. (C) 2010 Elsevier B.V. All rights reserved.