Bentonite is a potential buffer material of multi-barrier systems in high-level radioactive wastes repository. Montmorillonite, the main constituent of the bentonite, is 2:1 type aluminosilicate clay mineral with high swelling capacity and low permeability. Montmorillonite alteration under alkaline and saline conditions may affect the physico-chemical properties of the bentonite buffer. In this study, montmorillonite alteration by interaction with synthetic alkaline and saline solution and its retention capacity for cesium and iodide were investigated. The experiments were performed in three different batches (Milli-Q water, alkaline water, and saline water) doped with cesium and iodide for 7 days. Alteration characteristics and nuclide retention capacity of original- and reacted bentonite was analyzed by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscope (SEM), Nuclear Magnetic Resonance (NMR) and Cation Exchange Capacity (CEC) analysis. From the results, cesium retention occurred differently depending on the presence of competing ions such as K, Na, and Mg ions in synthetic solutions, while iodide was negligibly removed by bentonite. Montmorillonite alteration mainly occurred as cation exchange and zeolite minerals such as merlinoite and mordenite were new-formed during alkaline alteration of the montmorillonite. CEC value of reacted bentonite increased by formation of the zeolite minerals under alkaline conditions.