Unlike smectite, the surface characteristics of palygorskite remain underexplored for its potential application in environmental remediation. In this study, palygorskite from Western Australia was activated through thermal (300 °C for 4 h), acid (4 M HCl for 2 h at 70 °C) and acid-thermal (acid treatment followed by heating at 300 °C for 4 h) treatments, and the structural and physico-chemical characteristics were examined against the raw clay mineral. The influence of activation was systematically investigated using X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) spectroscopy, N₂ adsorption-desorption measurements and solid state ²⁷Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. The XRD patterns indicated preservation of the crystalline structure of palygorskite following all the treatments. These findings were supported by the Al (IV) and Al (VI) coordination peaks (chemical shift ~ 55 and 2.9 ppm, respectively) which were unaltered in the ²⁷Al MAS NMR spectra of the samples. The acid-thermal activated palygorskite exhibited the highest specific surface area (152.7 m² g^{− 1}) and pore volume (0.2137 cm³ g^{− 1}) which respectively were 3-fold and 69% greater than the raw palygorskite. The potentiometric titration analyses highlighted the possible role of Al derivatives towards development of the surface charge of the activated palygorskites. Electrokinetic studies described the stability of the activated products (zeta potential values ranging from - 5 mV to - 32 mV) at different electrolyte (NaNO₃) concentrations. Combined acid-thermal activated palygorskite displayed a stronger specific adsorption of multivalent cations, and held a direct relevance to environmental remediation. Findings of this study will assist in the development of palygorskite-based adsorbents for heavy metal contaminants remediation.