AbstractThis study investigates the synthesis and characterization of Al2O3 nanoparticles derived from multilayered packaging (MLP) waste, specifically postconsumer coffee capsules, and evaluates their efficacy in fluoride adsorption from aqueous solutions. The nanoparticles were synthesized using a facile thermal degradation technique followed by leaching and precipitation processes. Characterization techniques, including inductively coupled plasma‐mass spectroscopy, XRF, Fourier transform infrared spectroscopy, X‐ray diffraction, and transmission electron microscope, confirmed the formation of γ‐Al2O3 nanoparticles with a cubic crystal structure. The adsorption process was found to be endothermic and spontaneous, with a maximum adsorption capacity of 9.60 mg/g. Kinetic studies revealed that the pseudo‐second order model best described the adsorption process, indicating a complex multistep mechanism involving both physisorption in the initial rapid adsorption and chemisorption in the latter slower phase. The Freundlich–Langmuir isotherm provided the best fit for equilibrium data suggesting a complex adsorption mechanism involving both homogeneous and heterogeneous surface interactions. The presence of competing anions, particularly carbonate and phosphate, significantly affected the adsorption efficiency. This research demonstrates the potential of upcycling MLP waste into valuable adsorbents for wastewater treatment applications, offering both environmental and economic benefits.