This study assessed the performance of residual soils with regard to their macrostructural and microstructural properties and compatibility with leachate in pursuit of exploring alternative cost-effective and efficient landfill liner materials. A series of laboratory investigations was conducted on three residual soil samples by using tap water and leachate as permeation fluid to achieve the objectives of the study. The zeta potential measurements revealed that the presence of multivalent cations in the leachate decreased the diffuse double layer (DDL) thickness around the soil particles. The reduced DDL thickness caused a decrease in Atterberg limits of soil-leachate samples and changes in the classification of fine fractions. Additionally, the effects of pore clogging attributed to chemical precipitation and bioclogging were responsible for the reduction in measured hydraulic conductivities of soil-leachate samples. These effects can be clearly observed from the field-emission scanning electron microscopy images of soil-leachate samples with the appearance of less visible voids that led to a more compact and dense structure. The formation of new non-clay minerals and associated changes in the Al and Si ratio as reflected in the x-ray diffraction diffractograms and energy-dispersive x-ray analyses, respectively, were attributed to the effects of chemical precipitation. This study concluded that S1 and S2 residual soil samples are potential landfill liner materials because they possess adequate grading characteristics, adequate unconfined compressive strength, low hydraulic conductivity, and good compatibility with leachate. In contrast, the S3 sample requires further treatment to enhance its properties in order to comply with the requirements of landfill liner materials.