Illite plays an essential role in arsenic (As) transportation in the subsurface. Despite extensive investigations into As adsorption onto illite, debates persist due to the absence of direct evidence revealing the underlying processes. In this research, we conducted batch experiments and employed spherical aberration-corrected scanning transmission electron microscope, X-ray absorption spectroscopy, and density functional theory-based calculations to elucidate the mechanisms for the adsorption of two major inorganic As species (As(III) and As(V)) onto illite. Experimental results indicate adsorption capacities of 0.251 and 0.667 μmol/g for As(III) and As(V) onto illite, respectively. As(III) adsorption occurs within 300 min, whereas As(V) is rapidly adsorbed within 500 min, after which it tends to stabilize. Both As species can adsorbed onto the basal surface via electrostatic forces, where cations act as a bridge, leading to specific-cation effects. Conversely, As adsorption onto the edge surface can be ascribed to inner-sphere complexes via As-O-Al bonds, causing a negatively shifted isoelectric point of illite. These mechanisms collectively account for the partially reversible adsorption and two-stage kinetics pattern. Finally, a process-based surface complexation model was developed to predict As adsorption onto illite, which includes the inner/outer-sphere complexation and monodentate/bidentate complexes.