Fluoride pollution in drinking water is a worldwide concern arises from natural and human actions. The excessive fluoride present in drinking water leads to fluorosis. In this study, dual polysaccharide biopolymers namely pectin and chitosan were incorporated with magnesia followed by imprinted with lanthanum and cerium ions gives PCML (pectin/chitosan/magnesia/lanthanum) and PCMC (pectin/chitosan/magnesia/cerium) hybrid materials for fluoride adsorption investigation. The enhanced defluoridation capacities (DCs) of PCML and PCMC composites were seen as 4.976 and 4.972 mg g−1 by 30 min individually. To decide the impact of various affecting parameters viz., dosage, initial fluoride concentration, pH, contact time and challenging anions were examined in batch method. The pH results show the utmost DCs of PCML and PCMC composites was noted at pH 6 and in co-ions experiments, the significant competition found with bicarbonate ion owing to the superior electronic building of bicarbonate ion. The defluoridation equilibrium data of PCML and PCMC composites follows Langmuir, pseudo-second-order and intraparticle diffusion models. The positive ΔH° value as 3.04 kJ mol−1 for PCML composite and 2.88 kJ mol−1 for PCMC composite were exposed that the endothermic nature of fluoride adsorption occurs onto PCML and PCMC composites. The defluoridation mechanism of PCML and PCMC composites were attained by complexation, ion-exchange and electrostatic interaction. The reusability results shows that the synthesized PCML and PCMC composites can be reused upto six cycles. Field trail result demonstrates the synthesized PCML and PCMC composites were applicable at field conditions by reducing fluoride concentration below 1.5 mg/L.