The loading dependence of self-diffusion coefficients (Ds) of NO2, SO2, and their equimolar binary mixture in MIL-47(V) have been investigated by using classical molecular dynamics (MD) simulations. TheDsof NO2are found to be two orders of magnitude greater than SO2at low loadings and temperatures, and itsDsdecreases monotonically with loading. TheDsof SO2exhibit two diffusion patterns, indicating the specific interaction between the gas molecules and the MIL-47(V) lattice. The maximum activation energy (Ea) in the pure component and in the mixture for SO2are 16.43 and 18.35 kJ mol−1, and for NO2are 2.69 and 1.89 kJ mol−1, respectively. It is shown that SO2requires more amount of energy than NO2to increase the diffusion rate. The radial distribution functions (RDFs) of gas–gas and gas–lattice indicate that the Oh of MIL-47(V) are preferential adsorption site for both NO2and SO2molecules. However, the presence of the hydrogen bonding (HB) interaction between the O of SO2and the H of MIL-47(V) and also their binding angle (θ(OHC)) of 120° with the linkers of lattice indicate a stronger binding interaction between the SO2and the MIL-47(V), but it does not occur with NO2. The jump-diffusion of SO2between adsorption sites within the lattice has been confirmed by the 2D density distribution plots. Moreover, the extraordinarily highSdifffor NO2/SO2of 623.4 shows that NO2can diffuse through the MIL-47(V) significantly faster than SO2, especially at low loading and temperature.