Excessive fluoride and phosphate in water may pose risks to human health and adversely affect the ecological environment. Adsorption methods are considered promising technologies for phosphorus and fluoride removal due to their simplicity of operation, low operational costs, and absence of secondary pollution. However, currently developed adsorbents still face challenges such as low adsorption capacity, poor resistance to interference, and limited selectivity. Herein, La-MOF/UiO-66 layered heterostructures were constructed by controlling the amount of methanol and formic acid with epitaxial growth method. La-MOF/UiO-66 with layered stacking and porous structure possess a synergistic effect of more open metal active centers, synergies in bimetallic centers. For the phosphate and fluoride elimination, La-MOF/UiO-66 exhibits outstanding adsorption performance and a broad applicable pH range. The co-existing ions experiments showed that the common anions had a tiny effect for the adsorption performance, demonstrating a high selectivity performance. This is due to the construction of this heterojunction maximizes the exposure of abundant Zr and La metal active sites within a confined space, thereby multiplying the number of adsorption sites. Furthermore, the abundant aperture structure generated by this structure facilitates substance transfer processes, effectively shortening the migration path of target pollutants into the deeper layers of the adsorbent, thereby increasing the adsorption rate. This research offers a reference for the establishment of MOF-on-MOF heterostructures and contributes to the advancement of eco-friendly adsorbent with potential applications.