Engineered synthetic liners on their own cannot protect the environment and human health against landfill leachate pollution. Despite their initial impermeability, they are susceptible to failure during and after installation and have no attenuation properties. Conversely, natural clay liners can attenuate leachate pollutants by sorption, redox transformations, biodegradation, precipitation, and ... [Show full abstract] filtration, decreasing the pollutant flux. Depending on the clay, significant differences exist in their shrinkage potential, sorption capacity, erosion resistance and permeability to fluids, which affects the suitability and performance of the potential clay liner. Here, the physico-chemical, mineralogical and geotechnical characteristics of four natural clayey substrata were compared to discuss their feasibility as landfill liners. To study their chemical compatibility with leachate and rainwater, hydraulic conductivities were measured every ≈2 days spread over 7 weeks of centrifugation at 25 gravities. At field-scale, this is equivalent to every 3.4 yrs spread over 80 yrs. All the clayey substrata had favourable properties for the attenuation of leachate pollutants, although different management options should be applied for each one. London Clay (smectite-rich) is the best material based on the sorption capacity, hydraulic conductivity and low erodibility, but has the greatest susceptibility to excessive shrinkage and alterable clay minerals that partially collapse to illitic structures. Oxford Clay (illite rich) is the best material for buffering acid leachates and supporting degradation of organic compounds. The Coal Measures Clays (kaoline-rich) have the lowest sorption capacity, but also the lowest plasticity and have the most resistant clay minerals to alteration by leachate exposure.