The sorption of Ni(II) on a calcareous aridisol (CA) soil, one of the major soil types in northwestern China, was investigated using batch and extended X-ray absorption fine structure (EXAFS) approaches in a 0.01 mol/L NaClO4 solution at different pH values (6.0-10.0), temperatures (25-60 °C) and contact times (2-15 days). Under alkaline conditions, EXAFS analysis showed that the interatomic distances between Ni and O atoms (RNi-O) were approximately 2.04 Å with a typical coordination number (CN) of ~6.0 O atoms in the contact time range from 2 to 15 days. The RNi-Ni (~3.07 Å) suggested that the structure of the Ni(II) adsorbed on the CA soil was basically the same as that of Ni(OH)2(s), while the Ni-Al shell (RNi-Al ~3.16 Å) gradually formed and grew with the increasing contact time. Under weakly acidic conditions, the sorption mechanism of Ni(II) on the CA soil possibly included at least two processes: (i) a fast accumulation dominated by ion exchange and surface complexation and (ii) the formation of a Ni-Al LDH phase over the long term. A high temperature is beneficial to the fixation of Ni(II) on the CA soil and the formation of a Ni-Al LDH.