The biosorption ability of Lemna gibba for removing Ni2+ and Zn2+ ions in aqueous batch systems, both individually and simultaneously, was examined. The influences of solution pH and initial single and binary metal concentrations on equilibrium Ni2+ and Zn2+ biosorption was explored. The optimal solution pH for Ni2+ and Zn2+ biosorption was 6.0, for both the single and binary metal systems. Ni2+ and Zn2+ biosorption capacities increased with increasing initial metal concentrations. The presence of Zn2+ ions more adversely affected the biosorption of Ni2+ ions in the binary metal systems than vice versa. The single and binary biosorption isotherms of Ni2+ and Zn2+ revealed that L. gibba’s affinity for Zn2+ ions was higher than that for Ni2+ ions. The Redlich−Peterson and Freundlich isotherm models fit well to the experimental equilibrium data of Ni2+ ions, whereas Redlich−Peterson and Langmuir models better described the equilibrium data of Zn2+ ions in single metal systems. The modified Sips isotherm model best fit the competitive biosorption data of Ni2+-Zn2+ on L. gibba. FTIR analyses suggest the involvement of hemicellulose and cellulose in the biosorption of Ni2+ and Zn2+. The presence of Ni2+ and Zn2+ on the L.gibba surface was validated by SEM-EDX.