We describe the synthesis and corresponding full characterization of the set of UiO-66 metalorganic frameworks (MOFs) with 1,4-benzenedicarboxylate (C6H4(COOH)(2), hereafter H2BDC) and 1,4-naphthalenedicarboxylate (C10H6(COOH)(2), hereafter H2NDC) mixed linkers with NDC contents of 0, 25, 50, and 100%. Their structural (powder X-ray diffraction, PXRD), adsorptive (N-2, H-2, and CO2), vibrational (IR/Raman), and thermal stability (thermogravimetric analysis, TGA) properties quantitatively correlate with the NDC content in the material. The UiO-66 phase topology is conserved at all relative fractions of BDC/NDC. The comparison between the synchrotron radiation PXRD and 77 K N-2-adsorption isotherms obtained on the 50:50 BDC/NDC sample and on a mechanical mixture of the pure BDC and NDC samples univocally proves that in the mixed linkers of the MOFs the BDC and NDC linkers are shared in each MOF crystal, discarding the hypothesis of two independent phases, where each crystal contains only BDC or NDC linkers. The careful tuning of the NDC content opens a way for controlled alteration of the sorption properties of the resulting material as testified by the H-2-adsorption experiments, showing that the relative ranking of the materials in H-2 adsorption is different in different equilibrium-pressure ranges: at low pressures, 100NDC is the most efficient sample, while with increasing pressure, its relative performance progressively declines; at high pressures, the ranking follows the BDC content, reflecting the larger internal pore volume available in the MOFs with a higher fraction of smaller linkers. The H-2-adsorption isotherms normalized by the sample BrunauerEmmettTeller specific surface area show, in the whole pressure range, that the surface-area-specific H-2-adsorption capabilities in UiO-66 MOFs increase progressively with increasing NDC content. Density functional theory calculations, using the hybrid B3LYP exchange correlation functional and quadruple-zeta with four polarization functions (QZ4P) basis set, show that the interaction of H-2 with the H2NDC linker results in an adsorption energy larger by about 15% with respect to that calculated for adsorption on the H2BDC linker.