Significant chemical influence on the swelling potential of MX-80 bentonite was observed during swelling tests where specimens were hydrated with highly concentrated brine. The maximum swelling pressure for specimens hydrated with brine was about 30% of the maximum swelling pressure for the same specimens hydrated with de-ionized water. The maximum swelling pressure was attained within tens of hours of brine infiltration and further decreased by half within a year. A fully coupled hydro–mechanical–chemical (HMC) dual-porosity model is proposed in this paper to interpret the swelling behaviour of MX-80 when infiltrated with brine. The dependence of hydraulic and mechanical properties on such factors as porosity, salinity and water content was investigated. A nonlinear elastic constitutive model was proposed to correlate the swelling pressure with the variation in the microporosity. The chemical effects on the mechanical behaviour were coupled at the micropore level. A number of relationships have been developed for MX-80, i.e. micropore permeability as a function of void ratio, water retention characteristics of micropores and macropores, micropore dependence on water content and the diffusion coefficients of the two types of pore structure. The proposed model was successful in reproducing both quantitatively and qualitatively the experimental results from two sets of infiltration experiments on compacted MX-80 bentonite.