[en] A structural study of Pt nano-catalysts is presented in the paper. The innovation in the case of the considered catalytic materials resides in the use a meso-microporous inorganic matrix of heteropolyacid salt of composition X_2_._5H_0_._5YMo_1_2O_4_0 where X = Rb, Cs and Y = P, Si as a catalyst support. Metallic nanoparticles were created by platinum ions reduction in a hot H_2/Argon stream and were mainly located into matrix pores. As the porous structure can be controlled by the type and content of the cation used, the desired/optimal Pt nanoparticle size can be precisely defined by using a proper heteropolyacid salt composition. Multiple-scattering extended X-ray absorption fine structure (MS EXAFS) analysis was applied to obtain the relation between the matrix composition and the size of the catalyst nanoparticles. The results showed that it was only the secondary structure form of the heteropolymolybdate salt (i.e. Rb or Cs cations) that influenced the metallic nanoparticle size. The smaller the X atom ionic radii, the larger the mean diameter of the embedded Pt nanoparticles.