Ethanol is a versatile biofuel and industrial solvent widely used in pharmaceuticals, cosmetics, food and beverages, and chemical industries. Achieving high-purity ethanol remains a challenge due to the formation of ethanol–water azeotropes, which limit conventional distillation methods. This study investigates the effectiveness of KCl-assisted adsorptive distillation using natural packing materials—zeolite stones and Bio Ring Super—in enhancing ethanol purification. The objectives were to examine the characteristics of the packing materials, evaluate the effects of KCl addition, and assess the influence of packing height on ethanol concentration. A 10% ethanol solution was distilled using columns packed with either zeolite or Bio Ring Super stones, with and without the addition of KCl (0 g and 10 g). The final ethanol concentration was measured using a pycnometer and alcohol meter. Results indicated that the addition of 10 g KCl significantly increased ethanol purity by promoting salting-out effects, which enhanced separation efficiency. Among the packing materials, Bio Ring Super exhibited superior performance compared to zeolite, yielding the highest ethanol concentration in the distillate. Moreover, the combination of KCl addition and optimized packing height further improved ethanol recovery, demonstrating a more energy-efficient and cost-effective approach compared to conventional methods. These findings highlight the potential of KCl- assisted adsorptive distillation with Bio Ring Super packing as a sustainable and effective strategy for producing high-purity ethanol from biomass, offering promising applications in biofuel and industrial sectors.