Co, Ni and Mn K-edge XAFS investigation of LiCo1/3Ni1/3Mn1/3O2 as alternative cathode material to commercially used LiCoO2 in lithium rechargeable battery has been performed. Parameters of a local atomic structure such as radii of metal–oxygen and metal–metal coordination shells and disorder in those shells have been determined. It has been found that the radius of the first coordination shell (metal–oxygen) as well as a local disorder in the second shell (metal–metal) around each of the 3d-metals are in a good agreement with obtained for superlattice model of [√3×√3] R30° type in triangular lattice of sites by first principle calculation. Other parameters of the local atomic structure around Co, Ni and Mn atoms do not provide evidence for presence of superstructure in LiCo1/3Ni1/3Mn1/3O2.