The chemical and physical properties of 20 biochars produced at 350, 450, 550 and 650 °C were investigated to determine the key roles they play in the sorption and desorption of three potentially toxic elements (Pb, Cd, As). Biochar surfaces were studied using scanning electron microscopy, Fourier transform infra-red spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Organic functional groups (e.g. single bondCOOH, Cdouble bond; length as m-dashO, Csingle bondX), inorganic minerals (CaCO3, SiO2, Ca2Si5O10·3H2O) and cations (K+, Ca2+, Mg2+, Na+) controlled PTE sorption significantly while physical properties (morphology, surface area) showed little influence on the sorption of potentially toxic elements. Four major mechanisms accounted for the exceptionally high Pb(II) sorption by all 20 biochars (97.5–99.8%) while Cd(II) and As(III) sorption (