Keggin-type molybdophosphoric acid, molybdophosphoric salt and vanadium incorporated molybdophosphoric salt supported on the modified kaolin (MK) were investigated as redox co-catalysts for the oxidative carbonylation of phenol to diphenyl carbonate (DPC) in the absence of solvent. The 20 wt.% of MnAMPV5 (one kind of vanadium incorporated molybdophosphoric salt) loaded on MK showed the highest catalytic activity with the yield of 24.68% and a TON of 306, while the selectivity amounts to nearly 100% in all the carbonylation reactions. The catalysts were characterized by XRD, BET, XPS and H2-TPR. The reusability study showed that the catalysts were stable and active.