Europium(III), i.e., Eu(III), is chemically analogous to the trivalent lanthanides (Ln) and actinides (An). A good understanding of the adsorption behaviour of Eu(III) on mica group minerals is critical to the safety evaluation of the radioactive contamination. Nevertheless, the structural complexity of micaceous minerals makes it difficult to draw a consistent conclusion in the study of Eu(III) migration. In this work, we contrastively studied Eu(III) adsorption on dioctahedral muscovite and trioctahedral phlogopite as functions of pH, ionic strength, background electrolytes, interaction sequence, and fulvic acid (FA). Batch experiments showed that Eu(III) adsorption on both micas was strongly dependent on pH but quite independent on ionic strength that is determined by Na⁺. Planar sites are available on both muscovite and phlogopite while interlayer sites only on phlogopite under Na⁺ and Ca²⁺ electrolytes (not for K⁺ and Cs⁺). An interlayer expansion of phlogopite, as indicated by a newly appeared diffraction peak at ~6° 2-theta, occurred along with Eu(III) adsorption, which was also confirmed by transmission electron microscopy. Furthermore, the initial Eu(III) concentrations, the concentration ratios between Eu(III) and Cs⁺, and the reaction sequences of Eu(III)-electrolytes-FA affected both the adsorption behaviour of Eu(III) and reversely the structural alteration of phlogopite. The sequential extraction showed that the adsorbed Eu(III) was mainly in the ion-exchangeable form while the addition of FA could increase the portion of coordinative species. The currently proposed Eu(III) adsorption mechanism can shed new light on predicting the migration of Ln/An(III) at the mica-rich solid-liquid interface on a molecular scale.