The adsorption of molecular hydrogen in the Prussian blue analogue Cu3[Co(CN)6]2 was investigated using high-resolution neutron powder diffraction and neutron vibrational spectroscopy. Rietveld structural refinement of the neutron data for hydrogen loadings of 1, 2, and ∼2.3 H2/Cu showed that the hydrogen was absorbed at two sites within the structure. The most prominent adsorption site, located at the (1/4, 1/4, 1/4) crystallographic site, was an interstitial location within the structure. The second adsorption site was associated with exposed Cu2+ ion coordination sites that result from the presence of [Co(CN)6]3- vacancies within the structure of the material. The rotational−vibrational density of states of the adsorbed hydrogen was probed using neutron vibrational spectroscopy and showed a range of local binding potentials for the adsorbed hydrogen.