Zirconium-based metal-organic frameworks (MOFs) are candidate materials for effective nerve agent detoxification due to their thermo- and water stability as well as high density of catalytic Zr sites. However, as high-porosity materials, most of the active sites of Zr-MOFs can only be accessed by diffusion into the crystal interior. Therefore, the transport of nerve agents in nanopores is an important factor in the catalytic performance of Zr-MOFs. Here, we investigated the transport process and mechanism of a vapor-phase nerve agent simulant, dimethyl methyl phosphonate (DMMP), through a representative Zr-MOF, NU-1008, under practical conditions of varying humidity. Confocal Raman microscopy was used to monitor the transport of DMMP vapor through individual NU-1008 crystallites, where the relative humidity (RH) of the environment was tuned to understand the impact of water. Counterintuitively, water in the MOF channels, instead of blocking DMMP transport, assists DMMP diffusion; indeed, the transport diffusivity (Dt) of DMMP in NU-1008 is one order of magnitude higher at 70% than 0% RH. To understand the mechanism, magic angle spinning NMR and molecular dynamics simulations were performed and suggested that high water content in the channels prevents DMMP from hydrogen-bonding with the nodes, allowing for faster diffusion of DMMP in the channels. The simulated self-diffusivity (Ds) of DMMP is observed to be concentration-dependent. At low loading of DMMP, Ds is higher at 70% RH than 0% RH, while at high loadings the trend reverses due to the DMMP aggregation in water and the reduction of free volume in channels.