Porous materials, particularly metal-organic frameworks (MOFs), hold great promise for advanced applications. MIL-53(Al) is an exceptionally well-studied MOF that exhibits a phase transition upon guest capture─in this case, water─resulting in a dramatic change in the pore volume. Despite extensive studies, the structure of the water-loaded narrow-pore phase, MIL-53(Al)-np, remains controversial, particularly with respect to the positions of the adsorbed water molecules. We use terahertz spectroscopy, coupled with powder X-ray diffraction and density functional theory simulations, to unambiguously resolve this controversy. We show that the low-frequency (<100 cm-1) vibrational spectrum depends on weak long-range forces that are extremely sensitive to the orientation of the adsorbed water molecules. This enables definitively determining the correct structure of MIL-53(Al)-np while highlighting the extreme sensitivity of terahertz spectroscopy to bulk structure, suggesting its potential as a robust complement to X-ray diffraction for precise characterization of host-guest complexes.