In view of the animal feeds inevitably contaminated by multiple mycotoxins, eco-friendly and efficient palygorskite-montmorillonite (Pal-Mt) materials were prepared to remove polar aflatoxin B1 (AFB1) and weak polar zearalenone (ZEN) from mixed mycotoxins aqueous solution. The adsorption properties and bonding mechanisms between Pal-Mt materials and mycotoxins (AFB1 and ZEN) were investigated systematically. The as-prepared Pal-Mt showed excellent adsorption capacity for AFB1 and ZEN in single- and binary-mycotoxin systems, indicating the effectiveness of Pal-Mt acting as multiple mycotoxin adsorbents. The kinetics of adsorption for ZEN was fast due to the adsorption on the external surface (film and intraparticle diffusion), while AFB1 molecules permeated into mesopores after the external adsorption for the more planar structure. Adsorption isotherms demonstrated that heterogeneous surface adsorption appeared between Pal-Mt and AFB1, and monolayer adsorption occurred on Pal-Mt and ZEN for different polarities of mycotoxins. Thermodynamic parameters illustrated that the adsorption process of both AFB1 and ZEN onto Pal-Mt was spontaneous and endothermic. The adsorption mechanism studies suggested that hydrogen bonding, electrostatic attraction, calcium bridging linkage, and ion-dipole played fundamental roles in the interaction between Pal-Mt and these two mycotoxins.