A new aluminum naphthalenedicarboxylate Al(OH)(1,4-NDC)·2H 2O compound has been synthesized. The crystal structure exhibits a three-dimensional framework composed of infinite chains of corner-sharing octahedral Al(OH)2O4 with 1,4-naphthanedicarboxylate ligands forming two types of channels with squared-shape cross-section. The large channels present a cross-section of 7.7 × 7.7 Å2, while the small channels are about 3.0 × 3.0 Å2. When water molecules are removed, no structural transformation occurs, generating a robust structure with permanent porosity and remarkable thermal stability. 2D 1H-13C heteronuclear correlation NMR measurements, together with the application of Lee-Goldburg homonuclear decoupling, were applied, for the first time, to porous coordination polymers revealing the spatial relationships between the 1H and 13C spin-active nuclei of the framework. To demonstrate the open pore structure and the easy accessibility of the nanochannels to the gas phase, highly sensitive hyperpolarized (HP) xenon NMR, under extreme xenon dilution, has been applied. Xenon can diffuse selectively into the large nanochannels, while the small ones show no substantial uptake of xenon due to severe restrictions along the channels that prevent the diffusion. Two-dimensional exchange experiments showed the exchange time to be as short as 15 ms. Through variable-temperature HP 129Xe NMR experiments we were able to achieve an unprecedented description of the large nanochannel space and surface, a physisorption energy of 10 kJ mol-1, and the chemical shift value of xenon probing the internal surfaces. The large pore channels are straight, parallel, and independent, allowing one-dimensional anisotropic diffusion of gases and vapors. Their walls are composed of the naphthalene moieties that create an unique environment for selective sorption. These results prompted us to measure the storage capacity toward methanol, acetone, benzene, and carbon dioxide. The selective adsorption of methanol and acetone vs that of water, together with the permanent porosity and high thermal stability, makes this compound a suitable matrix for separation and purification.