The Keggin-type polyoxometalate (POM) PW12O403– and the catalytic complex Cp*Rh(bpydc)Cl2 (bpydc = 2,2′-bipyridine-5,5′-dicarboxylic acid) were coimmobilized in the Zr(IV) based metal organic framework UiO-67. The POM is encapsulated within the cavities of the MOF by in situ synthesis, and then, the Rh catalytic complex is introduced by postsynthetic linker exchange. Infrared and Raman spectroscopies, 31P and 13C MAS NMR, N2 adsorption isotherms, and X-ray diffraction indicate the structural integrity of all components (POM, Rh-complex and MOF) within the composite of interest (PW12,Cp*Rh)@UiO-67. DFT calculations identified two possible locations of the POM in the octahedral cavities of the MOF: one at the center of a UiO-67 pore with the Cp*Rh complex pointing toward an empty pore and one off-centered with the Cp*Rh pointing toward the POM. 31P–1H heteronuclear (HETCOR) experiments ascertained the two environments of the POM, equally distributed, with the POM in interaction either with the Cp* fragment or with the organic linker. In addition, Pair Distribution Function (PDF) data were collected on the POM@MOF composite and provided key evidence of the structural integrity of the POM once immobilized into the MOF. The photocatalytic activity of the (PW12,Cp*Rh)@UiO-67 composite for CO2 reduction into formate and hydrogen were evaluated. The formate production was doubled when compared with that observed with the POM-free Cp*Rh@UiO-67 catalyst and reached TONs as high as 175 when prepared as thin films, showing the beneficial influence of the POM. Finally, the stability of the composite was assessed by means of recyclability tests. The combination of XRD, IR, ICP, and PDF experiments was essential in confirming the integrity of the POM, the catalyst, and the MOF after catalysis.