It is reported in this paper the diphenylphosphinization of the groups of NH,NH2 on the surface of zirconium (tri-ethylenetetraaminoethylphosphonate-phosphate) supports Zr(HP04)2-x[O3PCH2CH2(NHCH2CH2)3NH2]X·H2O(ZP-TETAEPA) with ehlorodiphenylphosphine as the phosphining agent, the diphenylphosphinized support ZP-TETAEPA-DPP and its corre-sponding supported-palladium catalysts ZP-TETAEPA-DPP-Pd are prepared, and characterized by IR, TG, DTA and elementary analysis. In this paper, it is put stress on the investigation of the effect of the x value which is implicate the distribution of the active groups in the surface and interlayer on the catalytic reactivity of the carbonylation with the ZP-TETAEPA-DPP-Pd catalysts. The generalization of this effect existing in other zirconium phosphate-phosphonate catalysts was also discussed.