The remediation of wastewater containing Pb²⁺ has attracted much attention due to the harm of Pb²⁺ to the environment and human health. A promising adsorbent, functionalized montmorillonite modified with a ligand diethylenetriamine (DETA) was prepared under mild reaction conditions. The modified montmorillonite (DETA-MMT) and nature montmorillonite (Na-MMT) were then characterized with the help of XRD, FTIR, TG/DTG, and BET. It was revealed that the modifier DETA was successfully inserted into interlayers of montmorillonite, as demonstrated by the characterizations. Batch adsorption experiments of Pb²⁺ onto Na-MMT and DETA-MMT in solutions were studied as a function of various parameters, such as pH, contact time, initial concentration, and temperature. The maximum adsorption capacity of DETA-MMT was 61.1 mg g^–1, which had more than doubled compared with that of Na-MMT. The adsorption thermodynamics of Pb²⁺ by DETA-MMT was studied, and it showed a endothermic process. The adsorption kinetics of two samples both fit well with the pseudo-second-order model. The adsorption isotherms of Na-MMT and DETA-MMT can be well described by the Langmuir isotherm and Freundlich isotherm, respectively. Furthermore, the adsorbed Pb²⁺ onto DETA-MMT can hardly be dissolved under weak acidic condition (pH >4) according to the desorption experiments of simulated acid rain and Tessier’s sequential extraction procedure.