Rubidium and cesium are critical strategic elements, and their development and utilization are of great significance. In this study, a magnesium ammonium phosphate (MAP) adsorbent was prepared and characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area analysis, and Fourier transform infrared spectroscopy (FTIR). The adsorption performance of the adsorbent for Rb+ and Cs+ in solution was investigated. The results showed that the adsorbent exhibited high adsorption capacities of 2.83 mol/g for Rb+ and 4.37 mol/g for Cs+. In simulated brine, the adsorbent demonstrated excellent selectivity for Cs+. Kinetic and thermodynamic studies indicated that the adsorption process followed a pseudo-second order kinetic model and Langmuir isotherm model. The primary adsorption mechanism was an ion exchange. The development of this adsorbent holds significant promise for the extraction of rubidium and cesium from liquid resources.