The adsorptive removal of a pollutant from water is significantly affected by the presence of coexisting ions with various concentrations. Here, we have studied adsorption of arsenate [As(V)] by calcined Mg-Fe-(CO
3)-LDH in the presence of different cations (Mg
2+, Na
+, K
+, Ca
2+, and Fe
3+) and anions (CO
32‒, Cl
‒, PO
43‒, SO
42‒, and NO
3‒) with their different concentrations to simulate the field condition. The experimental results indicated that Ca
2+, Mg
2+, and Fe
3+ have a synergistic effect on removal efficiency of As(V), whereas PO
43‒ and CO
32‒ ions have a significant antagonistic impact. Overall, the order of inhibiting effect of coexisting anions on adsorption of As(V) was arrived as NO
3-˂Cl
-42-32-43-. Among them, competitive adsorption of phosphate with arsenic at different initial phosphate concentrations was found to be responsive to formulate a binary adsorption system. We have also developed a modified non-competitive Langmuir and Langmuir-Freundlich models; however, the modified competitive Langmuir model was arrived to be the most adequate model for this binary system. An Artificial Neural Network based multivariate prediction model was developed, delineating the impact of coexisting ions on the adsorption system. The proposed method may appropriately demonstrate the overall system and exhibited a significantly adequate prediction model with high R2, high F-value, and low error values.