The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline–acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K 1.38Na 0.05)(Al 2.87Mg 0.46Fe 3+ 0.39Fe 2+ 0.28Ti 0.07)[Si 7.02Al 0.98]O 20(OH) 4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0–4.25 (H 2SO 4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K + release rate was observed at I = 0.25 in 2–4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na + from the solution and K + from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1–4 in the higher ionic strength experiments and at pH ⩽3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R Al (dissolution rate calculated from steady state Al release) than R Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 ( I = 0.25) and 0.36 ( I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.