The temperature dependences of the long diagonals dMn–O of the MnO6 octahedron and the magnetic susceptibility χ of Nd2∕3Ca1∕3MnO3 in the temperature interval 100–290K are investigated. The functions dMn–O(T) and χ(T) are found to have anomalies in the charge-ordering range (Tco≈212K). The sharp decrease of the diagonal dMn–O2s agrees with phase-transition notions, according to which the spatial modulation of the charge density is due to the modulation of the Mn–Mn bond lengths. The most likely driving forces of the transition are the Peierls lattice instability and Jahn–Teller stability of the MnO6 octahedron at the Mn3+ ions. The hysteresis of the temperature dependence χ(T) in the paramagnetic region shows indirectly that structural phase separation occurs together with the transition. The parameters of the function χ(T) indicate that ferromagnetic clusters consisting of one, two, or three ion pairs Mn3+–Mn4+ form in the system in the temperature intervals 274K⩽T⩽290K, 224K⩽T⩽252K, and 130K⩽T⩽198K, respectively.