The paper is devoted to superexchange interaction in charge-ordered manganites. The charge and orbital superstructures of La0.333Ca 0.667MnO3 cause the frustrated magnetic structure. Within the framework of strong electron-lattice coupling, we can evaluate an orbital structure of the compound. The orbital and crystal structure parameters allow estimating the values of superexchange parameters and Neel temperature. The estimated superexchange parameters confirm the qualitative conclusions of experimental works about frustrated magnetic structure with magnetic supercell (3a×b×2c). © 2005 Elsevier B.V. All rights reserved.