Trioctahedral phyllosilicate minerals are widely distributed on the Earth’s surface, especially in soil. The mineral–water interfacial reaction of lizardite, chlorite and talc, with various structural properties (tetrahedral sheet, octahedral sheet, 1:1-type and 2:1-type interlayer domain/two-dimensional structural units), was carried out in sulfuric acid solution (1 mol L–1). The mineral samples were characterized by powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning and transmission electron microscopy and inductively coupled plasma mass spectrometry. The dissolution concentration, dissolution rate, dissolution rules and structural changes of the components during the dissolution processes of the various two-dimensional structural units were studied. The results show that the dissolution concentrations of Si and Mg in the sulfuric acid solution decrease in the following order: chlorite > lizardite > talc and lizardite > chlorite > talc. The dissolution rates of Si in chlorite and Mg in lizardite are the greatest, while talc is the most stable compared with lizardite and chlorite. With increasing interfacial reaction time and the dissolution of the ionic components of the minerals, the structure of lizardite is gradually destroyed; the structural destruction of chlorite is more obvious during the early stages of the reaction; and the structure of talc does not significantly change over the course of the entire reaction. By analysing the microtopography of the minerals, it was found that the structural failure of lizardite occurred from the surface to the interior. Chlorite had more structural defects and showed collapse of the layered structure during structural failure. The surface layer of talc decomposed by corrosion into a small lamellae structure attached to the surface, but there was no obvious structural change similar to those of lizardite and chlorite. The relationship between the evolution of composition and structure during the mineral–water interfacial reaction process with the two-dimensional structure layer type provides the mineralogical basis for studying the coupling mechanism of the migration and transformation of materials in key regions of the Earth.